CN109550499B - Catalyst for decomposing heavy components in neopentyl glycol synthetic waste liquid and preparation method and application thereof - Google Patents
Catalyst for decomposing heavy components in neopentyl glycol synthetic waste liquid and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000007788 liquid Substances 0.000 title claims abstract description 45
- 239000002699 waste material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910018516 Al—O Inorganic materials 0.000 claims abstract description 30
- 239000010949 copper Substances 0.000 claims abstract description 26
- 239000002585 base Substances 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 17
- 150000002148 esters Chemical class 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract 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 abstract description 13
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 13
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 12
- 229940116318 copper carbonate Drugs 0.000 claims abstract description 6
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 26
- 239000012065 filter cake Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000011777 magnesium Substances 0.000 claims description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 11
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical class [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Chemical class 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical group Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- 230000002431 foraging effect Effects 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 26
- 229910021641 deionized water Inorganic materials 0.000 description 26
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- RXGUIWHIADMCFC-UHFFFAOYSA-N 2-Methylpropyl 2-methylpropionate Chemical compound CC(C)COC(=O)C(C)C RXGUIWHIADMCFC-UHFFFAOYSA-N 0.000 description 6
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 6
- JJMOMMLADQPZNY-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanal Chemical compound OCC(C)(C)C=O JJMOMMLADQPZNY-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- SZCWBURCISJFEZ-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) 3-hydroxy-2,2-dimethylpropanoate Chemical compound OCC(C)(C)COC(=O)C(C)(C)CO SZCWBURCISJFEZ-UHFFFAOYSA-N 0.000 description 4
- HNWHVVWRJAXEEC-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) 2-methylpropanoate Chemical compound CC(C)C(=O)OCC(C)(C)CO HNWHVVWRJAXEEC-UHFFFAOYSA-N 0.000 description 3
- RDFQSFOGKVZWKF-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)C(O)=O RDFQSFOGKVZWKF-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VYZKQGGPNIFCLD-UHFFFAOYSA-N 3,3-dimethylhexane-2,2-diol Chemical compound CCCC(C)(C)C(C)(O)O VYZKQGGPNIFCLD-UHFFFAOYSA-N 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 Ester compounds Chemical class 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000006668 aldol addition reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- LBVWQMVSUSYKGQ-UHFFFAOYSA-J zirconium(4+) tetranitrite Chemical compound [Zr+4].[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O LBVWQMVSUSYKGQ-UHFFFAOYSA-J 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst for decomposing heavy components in neopentyl glycol synthetic waste liquid, and a preparation method and application thereof, wherein the catalyst is a Cu/Mg-Zr-Al-O composite base catalyst, a Cu element exists in the form of basic copper carbonate, the percentage composition of the Cu element is 10-30% of MgO and the percentage composition of the Cu element is ZrO based on the mass of the catalyst2 10～30％，Al2O3 10～30％，Cu2(OH)2CO330-50%. The composite alkali catalyst of the invention has two alkaline sites, one is from MgO and ZrO2And Al2O3And the other oxide is derived from basic copper carbonate, so that the catalyst has extremely strong alkalinity, has good catalytic effect on NPG (neopentyl glycol) (NPG) prepared by decomposing ester impurities in heavy component waste liquid of the NPG device, has the decomposition rate of various ester impurities up to over 90 percent, and can effectively improve the economic benefit of the device.
Description
Technical Field
The invention belongs to the technical field of catalysts and waste liquid treatment, and particularly relates to a catalyst for decomposing heavy components in neopentyl glycol synthetic waste liquid, and a preparation method and application thereof.
Background
Neopentyl glycol (NPG) is dihydric alcohol with a neopentyl structure, and two primary alcoholic hydroxyl groups are arranged at symmetrical positions in a molecule of the neopentyl glycol, so that the neopentyl glycol has good chemical reaction performance, and subsequent products prepared from the neopentyl glycol have excellent thermal stability, light resistance and the like. Neopentyl glycol is used mainly for the production of polyester resins, polyurethanes, powder coatings, synthetic lubricants and other fine chemicals.
The production of neopentyl glycol is generally carried out in two steps, firstly, Isobutyraldehyde (IBA) and formaldehyde are subjected to aldol addition reaction under the action of a basic catalyst to generate hydroxypivalaldehyde, and then neopentyl glycol is prepared from the hydroxypivalaldehyde. The production method for preparing neopentyl glycol from hydroxypivalaldehyde mainly comprises two production methods, wherein one method is to carry out disproportionation reaction on hydroxypivalaldehyde and formaldehyde under the action of an alkaline catalyst to generate neopentyl glycol and simultaneously produce sodium formate as a byproduct; one is the preparation of neopentyl glycol by hydrogenation of hydroxypivalaldehyde over a heterogeneous catalyst. In the above-mentioned NPG production process, heavy components such as NPG isobutyrate and NPG hydroxypivalate are produced, and then they are passed through a rectifying tower to make heavy component removal separation. Ester compounds such as neopentyl glycol hydroxypivalate, neopentyl glycol isobutyrate and isobutyl isobutyrate in heavy components generated in the NPG production process have excellent thermal stability and hydrolysis resistance, and are difficult to hydrolyze under the action of a common alkaline catalyst, so that the heavy components can only be used as waste liquid for low-price sale treatment or directly subjected to incineration treatment under the existing conditions, and resource utilization cannot be realized. In order to reduce the production cost of NPG and realize the effective utilization of heavy components, a heavy component resource utilization process needs to be developed urgently.
The solid base catalyst can effectively catalyze the hydrolysis of ester substances, and the patent CN101972642B discloses a series of composite solid base catalysts (ZnO/KF, ZnO/K) based on ZnO2CO3Etc.); CN103880670B discloses CaO-ZrO2A preparation method of the solid base catalyst; patent CN1317357C discloses a composite solid base catalyst composed of alkaline earth metal and alkali metal oxide, one or more of alkaline earth metal Mg, Ca, Sr and Ba, and alkali metal is one or more of Li, Na, K and Rb. However, the solid base catalysts have insufficient alkaline sites, and the conversion rate of the solid base catalysts for ester decomposition is low. Therefore, in order to realize efficient decomposition and effective recovery of ester impurities in the NPG waste liquid, the development of a catalyst with higher alkalinity is very important.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a catalyst for decomposing heavy components in neopentyl glycol synthetic waste liquid, wherein the catalyst is a Cu/Mg-Zr-Al-O composite alkali catalyst, has extremely strong alkalinity, and can be applied to the preparation of NPG (N-propyl glycol) by decomposing ester impurities in the heavy component waste liquid of an NPG device.
Meanwhile, the invention also provides a preparation method and application of the catalyst, and the catalyst is used for decomposing ester heavy components such as NPG isobutyrate and neopentyl glycol hydroxypivalate in the neopentyl glycol synthetic waste liquid to obtain a product NPG, so that the yield of an NPG device can be improved, and the economic benefit of a production device can be improved.
The technical scheme of the invention is as follows:
a catalyst for decomposing heavy components in neopentyl glycol synthetic waste liquid is a Cu/Mg-Zr-Al-O composite base catalyst, wherein a Cu element exists in the form of basic copper carbonate and is loaded on Mg-Zr-Al-O solid base.
The catalyst for decomposing heavy components in the neopentyl glycol synthetic waste liquid comprises, by mass, 10-30% of MgO, preferably 15-25%; ZrO (ZrO)210-30%, preferably 10-20%; al (Al)2O310-30%, preferably 10-20%; cu2(OH)2CO330 to 50%, preferably 35 to 45%.
The catalyst for decomposing heavy components in neopentyl glycol synthetic waste liquid has a specific surface area of 300-500 m2The pore radius is 30-150 nm, the active components are uniformly distributed, and the atom utilization rate is high.
The neopentyl glycol synthetic waste liquid is a by-product generated by condensation reaction and/or hydrogenation reaction of formaldehyde and isobutyraldehyde in the preparation process of neopentyl glycol. The heavy components in the waste liquid comprise the following components in percentage by mass based on the total mass of the heavy components: 50-70% of neopentyl glycol hydroxypivalate, 3-5% of neopentyl glycol isobutyrate, 3-5% of isobutyl isobutyrate, 20-40% of neopentyl glycol and the balance of impurities such as trimethylpentanediol, hydroxypivalic acid and the like, wherein the total content is 100%.
The preparation method of the catalyst for decomposing heavy components in the neopentyl glycol synthetic waste liquid comprises the following steps:
(1) adding soluble salts of magnesium, zirconium and aluminum into water for dissolving to obtain a solution A; dissolving sodium hydroxide and sodium carbonate in water to obtain solution B;
(2) adding the solution A and the solution B into water, controlling the pH of the solution at 9-10 and the temperature at 40-60 ℃ in the feeding process, and stirring for 30-60 min after feeding is finished;
(3) putting the mixed solution stirred in the step (2) into a constant temperature tank for aging, then carrying out suction filtration and washing with water to neutrality, and drying and roasting a filter cake to obtain Mg-Zr-Al-O solid alkali;
(4) and (3) soaking the Mg-Zr-Al-O solid alkali in a soluble salt water solution of copper, and roasting in a carbon dioxide atmosphere to prepare the catalyst for decomposing heavy components in the neopentyl glycol synthetic waste liquid.
In the step (1), the soluble salt of magnesium is selected from magnesium chloride, magnesium sulfate and magnesium nitrate, preferably magnesium nitrate; the soluble salt of zirconium is selected from zirconium chloride, zirconium sulfate, zirconium nitrate, preferably zirconium nitrate; the soluble salt of aluminum is selected from aluminum chloride, aluminum sulfate, aluminum nitrate, preferably aluminum nitrate.
In the step (1), the molar ratio of magnesium, zirconium and aluminum is 1: 0.1-2.0: 0.2-2.5.
In the step (1), the molar ratio of sodium hydroxide to sodium carbonate is in the range of 0.5-1.0: 1.
in the step (1), the total mass of the sodium hydroxide and the sodium carbonate is 1-5 times, preferably 1-3.5 times of the total mass of the magnesium, the zirconium and the aluminum.
In the step (2), the solution A and the solution B are preferably dropwise added, and the dropwise adding sequence and the dropwise adding speed are not specifically required; the concentration of the solution A and the solution B is not required, and the solution A and the solution B can be dissolved completely.
In the step (2), the stirring speed is 400-600 r/min.
In the step (3), the aging temperature is 60-80 ℃, and the aging time is 16-24 h.
In the step (3), the drying temperature is 50-70 ℃, and the drying time is 16-24 hours; the roasting temperature is 600-800 ℃, and the roasting time is 6-8 h.
In the step (4), the concentration range of the soluble salt water solution of copper is 10-50 mol/L, equal-volume impregnation is preferred, and the impregnation time is 6-12 h; the soluble salt of copper is selected from copper chloride, copper sulfate and copper nitrate, preferably copper nitrate.
In the step (4), the roasting temperature is 60-80 ℃, and the roasting time is 6-8 h.
The invention relates to application of a catalyst for decomposing heavy components in neopentyl glycol synthetic waste liquid.
The method for decomposing the heavy components in the neopentyl glycol synthetic waste liquid by adopting the catalyst comprises the steps of adding the neopentyl glycol synthetic waste liquid and the catalyst for decomposing the heavy components in the neopentyl glycol synthetic waste liquid into a fixed bed reactor, carrying out ester decomposition reaction, and separating and recovering the neopentyl glycol after the reaction.
In the ester decomposition reaction process, the temperature of a reactor bed layer is controlled to be 80-150 ℃, the reaction pressure is 0.1-0.3 MpaG, and the liquid hourly space velocity is 1-3 h-1The reaction time is 2-4 h.
The catalyst is tabletted into particles of 20-40 meshes before use.
In the reaction of decomposing neopentyl glycol to synthesize waste liquid heavy components, the decomposition rate of each heavy component ester is 90-98%, and the NPG yield is 95-98%.
The technical scheme of the invention has the following beneficial effects:
(1) the catalyst is a composite base catalyst, has high specific surface area and larger pore channels, and is beneficial to uniform distribution of active components and molecular diffusion.
(2) The catalyst of the invention is Cu/Mg-Zr-Al-O solid base catalyst, MgO and ZrO2And Al2O3Has certain alkalinity, and Mg element can enter ZrO2The crystal lattice, which creates new basic sites, further enhances the catalyst basicity.
(3) In the catalyst, the Cu element exists in the form of basic copper carbonate, and has stronger alkalinity compared with oxides, thereby effectively promoting the decomposition of esters in neopentyl glycol synthetic waste liquid, being capable of being uniformly distributed on the surface of Mg-Zr-Al-O solid alkali, having higher dispersity and improving the utilization rate of alkaline sites.
(4) The catalyst is a Cu/Mg-Zr-Al-O composite base catalyst, and has two basic sites, namely, one is from MgO and ZrO2And Al2O3And secondly, the catalyst is derived from basic copper carbonate, so that the catalyst has extremely strong alkalinity, has good catalytic effect on NPG (nitrogen phosphorus G) prepared by decomposing ester impurities in heavy component waste liquid of an NPG device, and the decomposition rate of various ester impurities can reach more than 90%.
Detailed Description
The present invention is described in further detail below by way of specific examples.
In the examples and the comparative examples, the waste liquid of the synthesis of neopentyl glycol came from the neopentyl glycol installation in the industrial park of Wanhua chemical cigarette benches. The heavy components in the waste liquid comprise the following components in percentage by mass based on the total mass of the heavy components: 50-70% of neopentyl glycol hydroxypivalate, 3-5% of neopentyl glycol isobutyrate, 3-5% of isobutyl isobutyrate, 20-40% of neopentyl glycol and the balance of impurities such as trimethylpentanediol, hydroxypivalic acid and the like, wherein the total content is 100%.
The others are common commercial raw materials and are not limited by manufacturers.
The composition of the product was analyzed by gas chromatography in the examples and comparative examples, and the conditions of gas chromatography were as follows: an Agilent 7890B gas chromatograph is provided with a shunt/non-shunt sample inlet and an FID detector to detect organic matters;
a chromatographic column: Agilent-DB-1(50 m.times.320. mu. m.times.1.05 μm);
sample introduction amount: 0.5 mu L;
column temperature: keeping the temperature at 35 ℃ for 3 minutes, heating to 80 ℃ at 15 ℃/min, keeping the temperature for 1min, heating to 270 ℃ at 20 ℃/min, and keeping the temperature for 5 min;
sample inlet temperature: 300 ℃;
flow rate of spacer purge gas: 3.0 mL/min;
column flow rate (N2): 1 mL/min;
split-flow sample injection with a split-flow ratio of 30: 1;
a detector: 300 ℃;
hydrogen flow rate: 30 mL/min;
air flow rate: 400 mL/min;
tail gas blowing flow: 25 mL/min.
Example 1
Preparation of catalyst for decomposing heavy components in neopentyl glycol synthetic waste liquid
(1) Separately weigh Mg (NO)3)2·6H216.00g of O (molecular weight 256), Zr (NO)3)4·5H2O (molecular weight 429)3.49g and Al (NO)3)3·9H214.70g of O (molecular weight 375) were dissolved together in 100mL of deionized water to obtain solution A. 4.5g of sodium hydroxide and 12.0g of sodium carbonate are weighed and dissolved in 200mL of deionized water together to obtain a solution B.
(2) And (3) dropwise adding the solution A and the solution B into 100mL of deionized water, adjusting the dropping speed at any time to stabilize the pH value of the solution between 9 and 10, controlling the reaction temperature to be 50 ℃, and stirring at the rotating speed of 400r/min for 60min after dropwise adding.
(3) And putting the stirred mixed solution into a constant temperature tank, aging for 16h at the temperature of 70 ℃, carrying out suction filtration and washing with water until the pH value of the filtrate is 7. And drying the filter cake at the temperature of 60 ℃ for 20h, then putting the filter cake into a muffle furnace, and roasting the filter cake at the high temperature of 800 ℃ for 8h to obtain the Mg-Zr-Al-O solid alkali.
(4) Weighing Cu (NO)3)2·3H2Dissolving 9.81g of O (molecular weight 241) in 10mL of deionized water to obtain a copper nitrate solution, and then soaking the Mg-Zr-Al-O solid alkali in the copper nitrate solution for 6 hours in equal volume; roasting in carbon dioxide atmosphere at 70 ℃ for 8h to obtain the Cu/Mg-Zr-Al-O composite base catalyst 1.
Catalyst 1 comprises the following components: MgO content 25 wt%, ZrO210 wt% of Al2O320 wt% of Cu2(OH)2CO3The content is 45 wt%, and the specific surface area is 456m2The average pore radius is 76nm, and the active components are uniformly distributed.
The application of the catalyst comprises the following steps:
the catalyst in the embodiment 1 is used for decomposing heavy components in neopentyl glycol synthetic waste liquid, and the method is that the catalyst is tabletted into particles of 20-40 meshes before use, and a fixed bed reactor is used for operation. The catalyst is filled in a fixed bed reactor, and 500g of neopentyl glycol synthetic waste liquid is added into the fixed bed reactor to carry out decomposition reaction on heavy component waste liquid.
Reaction conditions are as follows: the reaction temperature is 120 ℃, the reaction pressure is 0.1MpaG, and the liquid hourly space velocity is 3h-1The reaction time was 2 hours. The evaluation results are shown in Table 1.
Example 2
Preparation of catalyst for decomposing heavy components in neopentyl glycol synthetic waste liquid
(1) Separately weigh MgSO4(molecular weight 120)3.00g, Zr (NO)3)4·5H2O (molecular weight 429)6.98g and AlCl3·6H2O (molecular weight 241)9.45g was dissolved in 100mL of deionized water to obtain solution A. Sodium hydroxide 5.0g and sodium carbonate 13.3g were weighed and dissolved together in 200mL of deionized water to obtain solution B.
(2) And (3) dropwise adding the solution A and the solution B into 100mL of deionized water, adjusting the dropping speed at any time to stabilize the pH value of the solution between 9 and 10, controlling the reaction temperature to be 40 ℃, and stirring at the rotating speed of 400r/min for 50min after dropwise adding.
(3) And putting the stirred mixed solution into a constant temperature tank, aging for 24 hours at the temperature of 60 ℃, carrying out suction filtration and washing with water until the pH value of the filtrate is 7.
And drying the filter cake at the temperature of 60 ℃ for 16h, then placing the filter cake into a muffle furnace, and roasting the filter cake at the high temperature of 700 ℃ for 7h to obtain the Mg-Zr-Al-O solid alkali.
(4) Weighing CuCl2·2H2Dissolving 7.74g of O (molecular weight 171) in 10mL of deionized water to obtain a copper nitrate solution, and then soaking the Mg-Zr-Al-O solid alkali in the copper nitrate solution for 8 hours in equal volume; roasting in a carbon dioxide atmosphere at the roasting temperature of 80 ℃ for 6 hours to obtain the Cu/Mg-Zr-Al-O composite base catalyst 1.
Catalyst 2 comprises the following components: MgO content 10 wt%, ZrO220 wt% of Al2O320 wt% of Cu2(OH)2CO3The content is 50 wt%, and the specific surface area is 483m2The average pore radius is 63nm, and the active components are uniformly distributed.
The application of the catalyst comprises the following steps:
the operation was the same as in example 1. The specific evaluation results are shown in Table 1.
Example 3
Preparation of catalyst for decomposing heavy components in neopentyl glycol synthetic waste liquid
(1) Separately weigh MgCl2·6H2O (molecular weight 203)15.23g, Zr (SO)4)2·4H2O (molecular weight 355)8.66g and Al (NO)3)3·9H27.35g of O (molecular weight 375) was dissolved together in 100mL of deionized water to obtain solution A. 3.5g of sodium hydroxide and 9.3g of sodium carbonate are weighed and dissolved in 200mL of deionized water together to obtain a solution B.
(2) And (3) dropwise adding the solution A and the solution B into 100mL of deionized water, adjusting the dropping speed at any time to stabilize the pH value of the solution between 9 and 10, controlling the reaction temperature to be 60 ℃, and stirring at the rotating speed of 600r/min for 30min after dropwise adding.
(3) And putting the stirred mixed solution into a constant temperature tank, aging for 16h at the temperature of 80 ℃, carrying out suction filtration and washing with water until the pH value of the filtrate is 7.
And drying the filter cake at the temperature of 70 ℃ for 16h, then putting the filter cake into a muffle furnace, and roasting the filter cake at the high temperature of 600 ℃ for 8h to obtain the Mg-Zr-Al-O solid alkali.
(4) Weighing Cu (NO)3)2·3H2Dissolving 6.54g of O (molecular weight 241) in 10mL of deionized water to obtain a copper nitrate solution, and then soaking the Mg-Zr-Al-O solid alkali in the copper nitrate solution for 10 hours in equal volume; roasting at 60 ℃ for 8h in a carbon dioxide atmosphere to obtain the Cu/Mg-Zr-Al-O composite base catalyst 1.
The catalyst 3 comprises the following components in percentage by weight: MgO content 30 wt%, ZrO230 wt% of Al2O3Content 10 wt%, Cu2(OH)2CO3The content is 30 wt%, and the specific surface area is 437m2The average pore radius is 85nm, and the active components are uniformly distributed.
The application of the catalyst comprises the following steps:
the operation was the same as in example 1. The specific evaluation results are shown in Table 1.
Example 4
Preparation of catalyst for decomposing heavy components in neopentyl glycol synthetic waste liquid
(1) Separately weigh Mg (NO)3)2·6H2O (molecular weight 256)9.60g, Zr (SO)4)2·4H2O (molecular weight 355)4.33g and AlCl3·6H2O (molecular weight 241)14.18g was dissolved in 100mL of deionized water to obtain solution A. 4.3g of sodium hydroxide and 11.5g of sodium carbonate are weighed and dissolved in 200mL of deionized water together to obtain a solution B.
(2) And dropwise adding the solution A and the solution B into 100mL of deionized water, adjusting the dropping speed at any time to stabilize the pH value of the solution between 9 and 10, controlling the reaction temperature to be 50 ℃, and stirring at the rotating speed of 500r/min for 45min after dropwise adding.
(3) And putting the stirred mixed solution into a constant temperature tank, aging for 20 hours at the temperature of 60 ℃, carrying out suction filtration and washing with water until the pH value of the filtrate is 7.
And drying the filter cake at the temperature of 50 ℃ for 24 hours, then putting the filter cake into a muffle furnace, and roasting the filter cake at the high temperature of 750 ℃ for 7 hours to obtain the Mg-Zr-Al-O solid alkali.
(4) Weighing CuSO4·5H2Dissolving 9.05g of O (molecular weight of 250) in 10mL of deionized water to obtain a copper nitrate solution, and then soaking the Mg-Zr-Al-O solid alkali in the copper nitrate solution for 12 hours in equal volume; roasting at 70 ℃ for 7h in a carbon dioxide atmosphere to obtain the Cu/Mg-Zr-Al-O composite base catalyst 1.
Catalyst 4 contains the following components: MgO content 15 wt%, ZrO2Content 15 wt%, Al2O330 wt% of Cu2(OH)2CO3The content is 40 wt%, and the specific surface area is 423m2The average pore radius is 98nm, and the active components are uniformly distributed.
The application of the catalyst comprises the following steps:
the operation was the same as in example 1. The specific evaluation results are shown in Table 1.
Comparative example 1
Preparation of catalyst for decomposing heavy components in neopentyl glycol synthetic waste liquid
(1) Separately weigh Mg (NO)3)2·6H2O (molecular weight 256)16.00g，Zr(NO3)4·5H2O (molecular weight 429)3.49g, Al (NO)3)3·9H2O (molecular weight 375)14.70g and Cu (NO)3)2·3H2O (molecular weight 241)13.60g was dissolved in 100mL of deionized water to obtain solution A. Sodium hydroxide 5.0g and sodium carbonate 13.3g were weighed and dissolved together in 200mL of deionized water to obtain solution B.
(2) And (3) dropwise adding the solution A and the solution B into 100mL of deionized water, adjusting the dropping speed at any time to stabilize the pH value of the solution between 9 and 10, controlling the reaction temperature to be 50 ℃, and stirring at the rotating speed of 450r/min for 50min after dropwise adding.
(3) And putting the stirred mixed solution into a constant temperature tank, aging for 20 hours at the temperature of 70 ℃, carrying out suction filtration and washing with water until the pH value of the filtrate is 7.
And drying the filter cake at the temperature of 60 ℃ for 20h, then placing the filter cake into a muffle furnace, and roasting the filter cake at the high temperature of 800 ℃ for 8h to obtain the Cu/Mg-Zr-Al-O solid alkali.
Catalyst 5 comprises the following components: MgO content 25 wt%, ZrO210 wt% of Al2O3The content is 20 wt% and the CuO content is 45 wt%.
The application of the catalyst comprises the following steps:
the operation was the same as in example 1. The specific evaluation results are shown in Table 1.
Comparative example 2:
(1) separately weigh Mg (NO)3)2·6H2O (molecular weight 256)25.60g, ZrCl4(molecular weight 233)5.68g and Al (NO)3)3·9H2O (molecular weight 375)22.06g were dissolved together in 100mg of deionized water to give solution A. Sodium hydroxide 5.0g and sodium carbonate 13.3g were weighed and dissolved together in 200mL of deionized water to obtain solution B.
(2) And dropwise adding the solution A and the solution B into 100mL of deionized water, adjusting the dropping speed at any time to stabilize the pH value of the solution between 9 and 10, controlling the reaction temperature to be about 50 ℃, and stirring at the rotating speed of 500r/min for 60min after dropwise adding.
(3) And putting the stirred mixed solution into a constant temperature tank, aging for 16h at the temperature of 80 ℃, carrying out suction filtration and washing with water until the pH value of the filtrate is about 7.
And drying the filter cake at 70 ℃ for 20h, then placing the filter cake into a muffle furnace, and roasting the filter cake at 750 ℃ for 8h to obtain the Mg-Zr-Al-O solid base catalyst 6.
The catalyst 6 comprises the following components in percentage by weight: MgO content 40 wt%, ZrO230 wt% of Al2O3The content is 30 wt%.
The application of the catalyst comprises the following steps:
the operation was the same as in example 1. The specific evaluation results are shown in Table 1.
Comparative example 3
Preparation of catalyst for decomposing heavy components in neopentyl glycol synthetic waste liquid
(1) Separately weigh MgSO4(molecular weight 120)9.00g, and AlCl3·6H2O (molecular weight 241)14.18g was dissolved in 100mL of deionized water to obtain solution A. Sodium hydroxide 5.0g and sodium carbonate 13.3g were weighed and dissolved together in 200mL of deionized water to obtain solution B.
(2) And dropwise adding the solution A and the solution B into 100mL of deionized water, adjusting the dropping speed at any time to stabilize the pH value of the solution between 9 and 10, controlling the reaction temperature to be about 40 ℃, and stirring at the rotating speed of 600r/min for 60min after dropwise adding.
(3) And putting the stirred mixed solution into a constant temperature tank, aging for 24 hours at the temperature of 60 ℃, carrying out suction filtration and washing with water until the pH value of the filtrate is about 7.
And drying the filter cake at the temperature of 60 ℃ for 16h, then placing the filter cake into a muffle furnace, and roasting the filter cake at the high temperature of 600 ℃ for 7h to obtain the Zr-Al-O solid alkali.
(4) Weighing CuCl2·2H26.20g of O (molecular weight 171) is dissolved in 100Mg of deionized water to obtain a copper chloride solution, and then the Mg-Al-O solid base is immersed in the copper chloride solution for 8 hours in equal volume; roasting in the atmosphere of carbon dioxide at the roasting temperature of 80 ℃ for 6 hours to obtain the Cu-Mg-Al-O composite base catalyst 7.
Catalyst 7 contains the following components: MgO content 30 wt%, Al2O330 wt% of Cu2(OH)2CO3The content is 40 wt%, and the specific surface area is 372m2G, average pore radius of 38nm, and the active components are uniformly distributed.
The application of the catalyst comprises the following steps:
the operation was the same as in example 1. The specific evaluation results are shown in Table 1.
TABLE 1 conversion of ester decomposition of catalyst
The above description is a preferred embodiment of the present invention, but the present invention is not limited to the disclosure of the embodiment. Any simple variation, modification or other equivalent substitution by a person skilled in the art without any inventive step falls within the scope of protection of the present invention, without leaving the core of the invention.
Claims (12)
1. A catalyst for decomposing heavy components in neopentyl glycol synthetic waste liquid is characterized in that: the catalyst is a Cu/Mg-Zr-Al-O composite base catalyst, wherein a Cu element exists in the form of basic copper carbonate and is loaded on Mg-Zr-Al-O solid base;
based on the mass of the catalyst, the percentage composition of the catalyst is 10-30 percent of MgO and ZrO2 10～30％，Al2O3 10～30％，Cu2(OH)2CO3 30～50％。
2. The catalyst of claim 1, wherein: based on the mass of the catalyst, the percentage composition of the catalyst is 15-25 percent of MgO; ZrO (ZrO)2 10～20％；Al2O3 10～20％；Cu2(OH)2CO3 35～45％。
3. The catalyst of claim 1, wherein: the specific surface area is 300-500 m2The pore radius is 30-150 nm.
4. A preparation method of the catalyst for decomposing heavy components in neopentyl glycol synthetic waste liquid according to any one of claims 1 to 3 is characterized by comprising the following steps:
(1) adding soluble salts of magnesium, zirconium and aluminum into water for dissolving to obtain a solution A; dissolving sodium hydroxide and sodium carbonate in water to obtain solution B;
(2) adding the solution A and the solution B into water, controlling the pH of the solution at 9-10 and the temperature at 40-60 ℃ in the feeding process, and stirring for 30-60 min after feeding is finished;
(3) putting the mixed solution stirred in the step (2) into a constant temperature tank for aging, then carrying out suction filtration and washing with water to neutrality, and drying and roasting a filter cake to obtain Mg-Zr-Al-O solid alkali;
(4) and (3) soaking the Mg-Zr-Al-O solid alkali in a soluble salt water solution of copper, and roasting in a carbon dioxide atmosphere to prepare the catalyst for decomposing heavy components in the neopentyl glycol synthetic waste liquid.
5. The method of claim 4, wherein: in the step (1), the soluble salt of magnesium is selected from magnesium chloride, magnesium sulfate and magnesium nitrate; the soluble salt of zirconium is selected from zirconium chloride, zirconium sulfate, zirconium nitrate; the soluble salt of aluminum is selected from aluminum chloride, aluminum sulfate and aluminum nitrate;
in the step (4), the soluble salt of copper is selected from copper chloride, copper sulfate and copper nitrate.
6. The method of claim 4, wherein: in the step (1), the molar ratio of magnesium, zirconium and aluminum is 1: 0.1-2.0: 0.2-2.5; the molar ratio of sodium hydroxide to sodium carbonate is in the range of 0.5-1.0: 1; the total mass of the sodium hydroxide and the sodium carbonate is 1-5 times of the total mass of the magnesium, the zirconium and the aluminum;
in the step (4), the concentration range of the soluble salt water solution of copper is 1-10 mol/L.
7. The method of claim 6, wherein: in the step (1), the total mass of the sodium hydroxide and the sodium carbonate is 1-3.5 times of the total mass of the magnesium, the zirconium and the aluminum.
8. The method of claim 6, wherein: in the step (4), equal-volume impregnation is adopted for 6-12 hours.
9. The method of claim 4, wherein:
in the step (2), the stirring speed is 400-600 r/min;
in the step (3), the aging temperature is 60-80 ℃, and the aging time is 16-24 h; the drying temperature is 50-70 ℃, and the drying time is 16-24 hours; the roasting temperature is 600-800 ℃, and the roasting time is 6-8 h;
in the step (4), the roasting temperature is 60-80 ℃, and the roasting time is 6-8 h.
10. A method for decomposing heavy components in neopentyl glycol synthetic waste liquid by using the catalyst of any one of claims 1 to 3 or the catalyst prepared by the method of any one of claims 4 to 7, is characterized in that: and adding the neopentyl glycol synthetic waste liquid and a catalyst for decomposing heavy components in the neopentyl glycol synthetic waste liquid into the fixed bed reactor, carrying out ester decomposition reaction, and separating and recovering the neopentyl glycol after the reaction.
11. The method of claim 10, wherein: in the ester decomposition reaction process, the temperature of a reactor bed layer is 80-150 ℃, the reaction pressure is 0.1-0.3 MpaG, and the liquid hourly space velocity is 1-3 h-1The reaction time is 2-4 h.
12. The method of claim 10, wherein: the catalyst is 20-40 mesh particles before use.
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Denomination of invention: The invention relates to a catalyst for decomposing heavy components in neopentyl glycol synthesis waste liquid and a preparation method and application thereof Effective date of registration: 20211123 Granted publication date: 20210723 Pledgee: Bank of China Limited by Share Ltd. Yantai branch Pledgor: Wanhua Chemical Group Co.,Ltd. Registration number: Y2021980013026 |
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