CN116196912B - Calcium-based solid base catalyst and preparation method and application thereof - Google Patents
Calcium-based solid base catalyst and preparation method and application thereof Download PDFInfo
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- CN116196912B CN116196912B CN202310150552.XA CN202310150552A CN116196912B CN 116196912 B CN116196912 B CN 116196912B CN 202310150552 A CN202310150552 A CN 202310150552A CN 116196912 B CN116196912 B CN 116196912B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 63
- 239000011575 calcium Substances 0.000 title claims abstract description 63
- 239000007787 solid Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000001035 drying Methods 0.000 claims abstract description 40
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 28
- 239000003225 biodiesel Substances 0.000 claims abstract description 27
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 23
- 239000000292 calcium oxide Substances 0.000 claims abstract description 22
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 22
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 20
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 17
- 238000007873 sieving Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 150000003751 zinc Chemical class 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 241000237502 Ostreidae Species 0.000 claims description 22
- 235000020636 oyster Nutrition 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 11
- 239000001099 ammonium carbonate Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000002585 base Substances 0.000 abstract description 51
- 239000002253 acid Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 6
- 235000012424 soybean oil Nutrition 0.000 description 6
- 239000003549 soybean oil Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 230000001680 brushing effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000010775 animal oil Substances 0.000 description 2
- FWAMCARPUFWASE-UHFFFAOYSA-N bromoethane;methanol Chemical compound OC.CCBr FWAMCARPUFWASE-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 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
- RDHPKYGYEGBMSE-VQEHIDDOSA-N bromoethane Chemical group C[13CH2]Br RDHPKYGYEGBMSE-VQEHIDDOSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005809 transesterification 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
- C11C3/126—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on other metals or derivates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a calcium-based solid base catalyst and a preparation method and application thereof, and belongs to the technical field of catalyst preparation. The preparation method of the calcium-based solid base catalyst comprises the following steps: (1) Adding oyster shell powder, alkaline silica sol and pore-forming agent into water, uniformly mixing, drying, calcining, cooling to room temperature, grinding and sieving to obtain a calcium oxide-loaded carrier; (2) Adding the supported calcium oxide carrier and zinc salt into water, reacting, filtering, washing, drying, heating, calcining and cooling to obtain a calcium-based solid base catalyst precursor; (3) Grinding the calcium-based solid base catalyst precursor, sieving, adding a methanol solution of bromoethane, reacting, filtering, and drying to obtain the calcium-based solid base catalyst. The calcium-based solid base catalyst has a porous structure, is enhanced in acid resistance, can be fully contacted with oily reactants, can provide sufficient alkaline active sites for catalytic reaction, is applied to biodiesel preparation, has the biodiesel yield of more than or equal to 96%, and can be repeatedly used for many times.
Description
Technical Field
The application belongs to the technical field of catalyst preparation, and particularly relates to a calcium-based solid base catalyst, and a preparation method and application thereof.
Background
The biodiesel is environment-friendly fuel oil which is processed by taking animal and vegetable oil as raw materials and can replace common diesel oil, can be mixed with the diesel oil in an internal combustion engine in a proper proportion, can also be directly added into a diesel engine for use, has good combustion performance, and can promote the engine to burn fully; the biodiesel has no sulfur and aromatic hydrocarbon, has high oxygen content (10%), can obviously reduce the emission of harmful substances in tail gas, has high flash point and low volatility, and has high safety in storage, transportation and use.
The biodiesel can be prepared by a catalytic or non-catalytic method, and the non-catalytic method has high energy consumption and large investment, so the catalyst catalyzed method is preferred for production. The catalytic method for producing biodiesel is divided into homogeneous catalysis and heterogeneous catalysis, and the catalysts used in the homogeneous catalysis are mainly strong acid and strong alkali, so that the method has the defects of high production cost, difficulty in separating products, large wastewater production amount and the like. Compared with the heterogeneous catalyst, after the reaction is finished, the product does not need to be washed with water, no waste water is generated, and the method is environment-friendly.
Biodiesel consists mainly of fatty acid alkyl esters derived from the esterification of free fatty acids and transesterification of glycerides, and alkaline earth metal oxides or basic oxides can be used as biodiesel heterogeneous catalysts.
As one of the main marine aquaculture varieties, the oyster juice is delicious, has a health care function, is deeply favored by consumers, but a large number of oyster shells are often directly discarded without treatment, emit unpleasant smell and have serious environmental pollution. In order to realize the recycling of oyster shell waste, researchers develop the oyster shell waste into building materials, acidic sulfate soil stabilizers, phosphate adsorbents and the like, but the added value of the product is not high, and the utilization rate of oyster shells is low. The main component of the oyster shell is calcium carbonate, and the calcium carbonate is converted into calcium oxide through high-temperature calcination and can be used as an ester exchange catalyst for biodiesel preparation, but the calcined oyster shell directly serves as a catalyst and has the problems of low activity, easiness in poisoning and deactivation of the catalyst, low recycling rate and the like.
Therefore, how to prepare a calcium-based solid base catalyst which has high activity and high stability and can be repeatedly used for multiple times has become a problem to be solved in the art.
Disclosure of Invention
The application aims to provide a calcium-based solid base catalyst, a preparation method and application thereof, so as to solve the problems in the prior art.
The application provides the following scheme:
a preparation method of a calcium-based solid base catalyst comprises the following steps:
(1) Adding oyster shell powder, alkaline silica sol and pore-forming agent into water, uniformly mixing, drying, calcining, cooling to room temperature, grinding and sieving to obtain a calcium oxide-loaded carrier;
(2) Adding the supported calcium oxide carrier and zinc salt into water, reacting, filtering, washing, drying, heating, calcining and cooling to obtain a calcium-based solid base catalyst precursor;
(3) Grinding the calcium-based solid base catalyst precursor, sieving, adding a methanol solution of bromoethane, reacting, filtering, and drying to obtain the calcium-based solid base catalyst.
Further, the preparation method of the oyster shell powder in the step (1) comprises the following steps: removing impurities on the surfaces of the oyster shells, washing with water, drying at 50 ℃ for 24 hours, crushing, and sieving with a 40-mesh sieve to obtain the oyster shell powder.
Further, the pore-forming agent in the step (1) is one of ammonium carbonate and ammonium bicarbonate.
Further, in the step (1), the feed liquid ratio of oyster shell powder, alkaline silica sol, pore-forming agent and water is as follows: (20-50) g, (60-80) g, and (10-30) g, and (100-200) mL.
Further, in the step (1), the drying temperature is 100-120 ℃ and the drying time is 2-5h; the calcination temperature is 900-950 ℃ and the calcination time is 4-6h.
Further, the zinc salt in the step (2) comprises one of zinc nitrate, zinc chloride and zinc acetate; the zinc salt accounts for 3-20% of the weight of the loaded calcium oxide carrier.
Further, the reaction temperature in the step (2) is 25-55 ℃ and the reaction time is 4-10h; the drying temperature is 105 ℃ and the drying time is 4-10 hours; the heating rate is 5-7 ℃/min; the calcination temperature is 900 ℃ and the calcination time is 2-5h.
Further, the feed liquid ratio of the calcium-based solid base catalyst precursor to the methanol solution of bromoethane in the step (3) is: (15-30) g and (20-40) mL; the mass concentration of the bromoethane in the methanol solution of the bromoethane is 0.1 percent; the reaction temperature is 50-60 ℃, the reaction time is 3-5h, the drying temperature is 100-120 ℃, and the drying time is 4-6h.
The application also provides a calcium-based solid base catalyst.
The application also provides application of the calcium-based solid base catalyst in biodiesel preparation.
The application has the beneficial effects that:
(1) The internal structure of the silica sol is a siloxane bond, in the calcination process, ammonium carbonate or ammonium bicarbonate generates carbon dioxide and ammonia gas, a porous grid structure formed under the action of the pore-forming agent is used as a carrier, caO generated by the oyster shell powder in the high-temperature calcination process is an alkaline activation center, and the addition of silicon promotes the formed Ca-O-Si bond to strengthen the stability of the catalyst, so that the prepared catalyst can be repeatedly used.
(2) The zinc source is loaded on the active center of CaO by a wet impregnation method, so that the acid resistance of the catalyst after loading the zinc source is obviously enhanced, and the catalytic activity is further improved.
(3) According to the calcium-based solid base catalyst provided by the application, both the carrier and the active center are hydrophilic and oleophobic, and the bromoethane is added to form hydrophobic membranes on the surfaces of the carrier and the active center, so that reactants are promoted to diffuse on the surface of the catalyst by a similar compatibility principle, the utilization rate of active sites is improved, and the catalytic activity is further increased, but when the addition amount of bromoethane is excessive, bromoethane is bonded to the surface of CaO through hydroxyl bonds, so that the active sites are greatly reduced, and the catalytic activity is reduced.
(4) The calcium-based solid base catalyst provided by the application has a porous structure, is enhanced in acid resistance, can be fully contacted with oily reactants, can provide sufficient alkaline active sites for catalytic reaction, has the biodiesel yield of more than or equal to 96%, and can be repeatedly used for many times.
(5) The calcium-based solid base catalyst provided by the application realizes the recycling of waste resources by recycling the waste oyster shells, and simultaneously effectively reduces environmental pollution.
Detailed Description
Various exemplary embodiments of the application will now be described in detail, which should not be considered as limiting the application, but rather as more detailed descriptions of certain aspects, features and embodiments of the application.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the application. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the application described herein without departing from the scope or spirit of the application. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present application. The specification and examples of the present application are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The normal temperature in the examples of the present application means 25.+ -. 2 ℃.
The embodiment of the application provides a preparation method of a calcium-based solid base catalyst, which comprises the following steps:
(1) Adding oyster shell powder, alkaline silica sol and pore-forming agent into water, uniformly mixing, drying, calcining, cooling to room temperature, grinding and sieving to obtain a calcium oxide-loaded carrier;
(2) Adding the supported calcium oxide carrier and zinc salt into water, reacting, filtering, washing, drying, heating, calcining and cooling to obtain a calcium-based solid base catalyst precursor;
(3) Grinding the calcium-based solid base catalyst precursor, sieving, adding a methanol solution of bromoethane, reacting, filtering, and drying to obtain the calcium-based solid base catalyst.
Further, the preparation method of the oyster shell powder in the step (1) comprises the following steps: removing impurities on the surfaces of the oyster shells, washing with water, drying at 50 ℃ for 24 hours, crushing, and sieving with a 40-mesh sieve to obtain the oyster shell powder. The pore-forming agent is one of ammonium carbonate and ammonium bicarbonate. The feed liquid ratio of the oyster shell powder, the alkaline silica sol, the pore-forming agent and the water is as follows: (20-50) g, (60-80) g, and (10-30) g, and (100-200) mL. The drying temperature is 100-120 ℃, and the drying time is 2-5h; the calcination temperature is 900-950 ℃ and the calcination time is 4-6h.
Further, the zinc salt in the step (2) comprises one of zinc nitrate, zinc chloride and zinc acetate; the zinc salt accounts for 3-20% of the weight of the loaded calcium oxide carrier. The reaction temperature is 25-55 ℃ and the reaction time is 4-10h; the drying temperature is 105 ℃ and the drying time is 4-10 hours; the heating rate is 5-7 ℃/min; the calcination temperature is 900 ℃ and the calcination time is 2-5h.
Further, the feed liquid ratio of the calcium-based solid base catalyst precursor to the methanol solution of bromoethane in the step (3) is: (15-30) g and (20-40) mL; the mass concentration of the bromoethane in the methanol solution of the bromoethane is 0.1 percent; the reaction temperature is 50-60 ℃, the reaction time is 3-5h, the drying temperature is 100-120 ℃, and the drying time is 4-6h.
The embodiment of the application also provides a calcium-based solid base catalyst.
The embodiment of the application also provides application of the calcium-based solid base catalyst in biodiesel preparation, which comprises the following specific preparation processes:
mixing oil and low-carbon alcohol according to a molar ratio of 1:6-1:18, adding 3-10wt% (the calcium-based solid base catalyst accounts for the mass of the oil) of the calcium-based solid base catalyst, and carrying out reflux reaction at a temperature of 45-70 ℃ for 1-5 hours; after the reaction is finished, centrifuging the mixture, wherein the upper layer is alcohol and byproduct glycerol, the middle layer is biodiesel, the lower layer is catalyst, separating out the catalyst, distilling the liquid product to recover methanol, standing the rest liquid for 24 hours, and separating the glycerol to obtain the biodiesel.
Further, the oil is one of animal oil, vegetable oil and waste edible oil, and the low-carbon alcohol is one of methanol, ethanol, propanol and butanol.
Unless otherwise specified, the raw materials of the application are all obtained by purchase.
Example 1
A preparation method of a calcium-based solid base catalyst comprises the following steps:
(1) And (3) brushing impurities such as soil on the surfaces of the oyster shells by using a brush, washing the oyster shells by using distilled water, draining, drying the oyster shells in an oven at 50 ℃ for 24 hours, crushing the oyster shells by using a hammer crusher, and sieving the oyster shells by using a 40-mesh sieve to obtain oyster shell powder.
(2) Adding 20g of oyster shell powder, 70g of alkaline silica sol and 10g of ammonium carbonate into 150mL of distilled water, stirring and mixing uniformly, drying for 3h at 110 ℃, calcining for 5h at 900 ℃, crushing, and sieving with a 100-mesh sieve to obtain the supported calcium oxide carrier.
(3) 15g of the supported calcium oxide carrier and 0.45g of zinc acetate are taken and added into 150mL of distilled water, the mixture is reacted for 8 hours under the constant temperature magnetic stirring condition of 25 ℃, filtered and washed until no zinc ions are detected, dried for 10 hours at 105 ℃, then heated to 900 ℃ at the heating rate of 5 ℃/min, kept for 5 hours, and cooled to room temperature, thus obtaining the calcium-based solid base catalyst precursor.
(4) 15g of the calcium-based solid base catalyst precursor was added to 20mL of a methanol solution of bromoethane (the mass concentration of bromoethane in the methanol solution of bromoethane is 0.1%), the mixture was refluxed at 50℃for 4 hours, filtered, and dried at 100℃for 5 hours to obtain a calcium-based solid base catalyst.
Example 2
A preparation method of a calcium-based solid base catalyst comprises the following steps:
(1) And (3) brushing impurities such as soil on the surfaces of the oyster shells by using a brush, washing the oyster shells by using distilled water, draining, drying the oyster shells in a drying oven at 50 ℃ for 24 hours, crushing the oyster shells by using a hammer crusher, and sieving the oyster shells by using a 40-mesh sieve to obtain oyster shell powder.
(2) Adding 30g of oyster shell powder, 60g of alkaline silica sol and 20g of ammonium bicarbonate into 100mL of distilled water, stirring and mixing uniformly, drying for 4 hours at 100 ℃, calcining for 4 hours at 950 ℃, crushing, and sieving with a 100-mesh sieve to obtain the supported calcium oxide carrier.
(3) Adding 30g of a supported calcium oxide carrier and 6g of zinc nitrate into 200mL of distilled water, reacting for 4 hours under the condition of constant temperature magnetic stirring at 55 ℃, filtering, washing until no zinc ions are detected, drying for 6 hours at 105 ℃, heating to 900 ℃ at the heating rate of 7 ℃/min, keeping for 2 hours, and cooling to room temperature to obtain the calcium-based solid base catalyst precursor.
(4) 30g of the calcium-based solid base catalyst precursor was added to 40mL of a methanol solution of bromoethane (the mass concentration of bromoethane in the methanol solution of bromoethane is 0.1%), the mixture was refluxed at 60℃for 3 hours, filtered, and dried at 110℃for 6 hours to obtain a calcium-based solid base catalyst.
Example 3
A preparation method of a calcium-based solid base catalyst comprises the following steps:
(1) And (3) brushing impurities such as soil on the surfaces of the oyster shells by using a brush, washing the oyster shells by using distilled water, draining, drying the oyster shells in an oven at 50 ℃ for 24 hours, crushing the oyster shells by using a hammer crusher, and sieving the oyster shells by using a 40-mesh sieve to obtain oyster shell powder.
(2) 50g of oyster shell powder, 75g of alkaline silica sol and 25g of ammonium carbonate are added into 200mL of distilled water, stirred and mixed uniformly, dried for 5 hours at 120 ℃, calcined for 6 hours at 920 ℃, crushed and sieved by a 100-mesh sieve, and the supported calcium oxide carrier is obtained.
(3) Adding 30g of a supported calcium oxide carrier and 3g of zinc chloride into 150mL of distilled water, reacting for 6 hours under the condition of constant temperature magnetic stirring at 35 ℃, filtering, washing until no zinc ions are detected, drying for 6 hours at 105 ℃, heating to 900 ℃ at the heating rate of 6 ℃/min, keeping for 3.5 hours, and cooling to room temperature to obtain the calcium-based solid base catalyst precursor.
(4) 20g of the calcium-based solid base catalyst precursor was added to 30mL of a methanol solution of bromoethane (the mass concentration of bromoethane in the methanol solution of bromoethane is 0.1%), the mixture was refluxed at 56℃for 5 hours, filtered, and dried at 120℃for 4 hours to obtain a calcium-based solid base catalyst.
Comparative example 1
The difference is that in the step (2), no alkaline silica sol is added as in example 1.
Comparative example 2
The procedure of example 1 was repeated except that a zinc source was not supported on the supported calcium oxide carrier, and that 20mL of a methanol solution of bromoethane (the mass concentration of bromoethane in the methanol solution of bromoethane was 0.1%) was directly added to 15g of the supported calcium oxide carrier, followed by reflux reaction at 50℃for 4 hours, filtration, and drying at 100℃for 5 hours to obtain a calcium-based solid base catalyst.
Comparative example 3
The difference from example 1 is that the volume of the bromoethane methanol solution in the step (4) is 15mL.
Comparative example 4
The difference from example 1 is that the volume of the bromoethane methanol solution in the step (4) is 48mL.
Effect verification
Verification example 1
The calcium-based solid base catalysts obtained in examples 1 to 3 and comparative examples 1 to 4 were used to prepare biodiesel, respectively, by the following steps:
(1) 50.0g (0.057 mol) of soybean oil and 27.3g (0.853 mol) of methanol were added to a three-necked flask, and then the calcium-based solid base catalysts obtained in examples 1 to 3 and comparative examples 1 to 4 were added respectively in an amount of 3% by weight of the soybean oil, and the mixture was refluxed at 65℃for 2.5 hours under magnetic stirring;
(2) Centrifuging after the reaction is finished, wherein the upper layer is methanol and byproduct glycerol, the middle layer is biodiesel, and the lower layer is a catalyst; separating the catalyst from the liquid product, distilling to recover methanol, standing the rest liquid for 24h, and separating glycerol to obtain biodiesel. The biodiesel conversions obtained by catalysis with the calcium-based solid base catalysts obtained in examples 1-3 and comparative examples 1-4 are shown in Table 1.
TABLE 1
Verification example 2
The calcium-based solid base catalyst obtained in the example 1 is used for preparing biodiesel, and the preparation method comprises the following steps:
(1) 50.0g (0.057 mol) of soybean oil and 38.3g (0.833 mol) of ethanol are added into a three-necked flask, then the calcium-based solid base catalyst obtained in example 1 is added according to 5 percent of the weight of the soybean oil, and reflux reaction is carried out for 2.5 hours at 65 ℃ under magnetic stirring;
(2) Centrifuging after the reaction is finished, wherein the upper layer is ethanol and byproduct glycerol, the middle layer is biodiesel, and the lower layer is a catalyst; separating the catalyst from the liquid product, distilling to recover ethanol, standing the rest liquid for 24h, and separating glycerol to obtain biodiesel.
The calcium-based solid base catalyst obtained in example 1 was reused 8 times and the biodiesel conversion per time was measured as shown in table 2.
The preparation method of biodiesel by adopting the calcium-based solid base catalyst obtained in the comparative example 1 comprises the following steps:
(1) 50.0g (0.057 mol) of soybean oil and 38.3g (0.833 mol) of ethanol are added into a three-necked flask, then the calcium-based solid base catalyst obtained in the comparative example 1 is added according to 5 percent of the weight of the soybean oil, and the mixture is subjected to reflux reaction for 2.5 hours at 65 ℃ under magnetic stirring;
(2) Centrifuging after the reaction is finished, wherein the upper layer is ethanol and byproduct glycerol, the middle layer is biodiesel, and the lower layer is a catalyst; separating the catalyst from the liquid product, distilling to recover ethanol, standing the rest liquid for 24h, and separating glycerol to obtain biodiesel.
The calcium-based solid base catalyst obtained in comparative example 1 was reused 8 times, and the conversion of biodiesel was measured each time, as shown in Table 2.
TABLE 2
The above embodiments are only illustrative of the preferred embodiments of the present application and are not intended to limit the scope of the present application, and various modifications and improvements made by those skilled in the art to the technical solutions of the present application should fall within the protection scope defined by the claims of the present application without departing from the design spirit of the present application.
Claims (6)
1. The preparation method of the calcium-based solid base catalyst is characterized by comprising the following steps of:
(1) Adding oyster shell powder, alkaline silica sol and pore-forming agent into water, uniformly mixing, drying, calcining, cooling to room temperature, grinding and sieving to obtain a calcium oxide-loaded carrier;
(2) Adding the supported calcium oxide carrier and zinc salt into water, reacting, filtering, washing, drying, heating, calcining and cooling to obtain a calcium-based solid base catalyst precursor;
(3) Grinding and sieving the calcium-based solid base catalyst precursor, adding a methanol solution of bromoethane, reacting, filtering and drying to obtain a calcium-based solid base catalyst;
the pore-forming agent in the step (1) is one of ammonium carbonate and ammonium bicarbonate;
in the step (1), the feed liquid ratio of oyster shell powder, alkaline silica sol, pore-forming agent and water is (20-50) g to (60-80) g to (10-30) g to (100-200) mL;
the zinc salt in the step (2) comprises one of zinc nitrate, zinc chloride and zinc acetate;
the zinc salt accounts for 3-20% of the weight of the loaded calcium oxide carrier;
the feed liquid ratio of the calcium-based solid base catalyst precursor to the methyl alcohol solution of bromoethane in the step (3) is (15-30) g to (20-40) mL; the reaction temperature is 50-60 ℃ and the reaction time is 3-5h.
2. The method for preparing the calcium-based solid base catalyst according to claim 1, wherein the preparation method of the oyster shell powder in the step (1) comprises the following steps: removing impurities on the surfaces of the oyster shells, washing with water, drying at 50 ℃ for 24 hours, crushing, and sieving with a 40-mesh sieve to obtain the oyster shell powder.
3. The method for preparing a calcium-based solid base catalyst according to claim 1, wherein the drying temperature in the step (1) is 100-120 ℃ and the drying time is 2-5 hours;
the calcination temperature is 900-950 ℃ and the calcination time is 4-6h.
4. The method for preparing a calcium-based solid base catalyst according to claim 1, wherein the reaction temperature in the step (2) is 25-55 ℃ and the reaction time is 4-10 hours;
the drying temperature is 105 ℃ and the drying time is 4-10 hours;
the heating rate is 5-7 ℃/min; the calcination temperature is 900 ℃ and the calcination time is 2-5h.
5. A calcium-based solid base catalyst prepared by the method for preparing a calcium-based solid base catalyst according to any one of claims 1 to 4.
6. Use of the calcium-based solid base catalyst of claim 5 in the preparation of biodiesel.
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