CN113788806A - A kind of method for preparing furfural by utilizing chitosan-based solid acid catalyst - Google Patents
A kind of method for preparing furfural by utilizing chitosan-based solid acid catalyst Download PDFInfo
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 239000011973 solid acid Substances 0.000 title claims abstract description 89
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 22
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 19
- 239000002699 waste material Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000003513 alkali Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 23
- 239000002028 Biomass Substances 0.000 claims abstract description 20
- 229920002488 Hemicellulose Polymers 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000011282 treatment Methods 0.000 claims abstract description 13
- 241000238424 Crustacea Species 0.000 claims abstract description 12
- 238000010306 acid treatment Methods 0.000 claims abstract description 12
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 239000000706 filtrate Substances 0.000 claims abstract description 3
- 238000005470 impregnation Methods 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000010902 straw Substances 0.000 claims description 16
- 229960001231 choline Drugs 0.000 claims description 14
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 14
- OASOQJKCZXXDMI-UHFFFAOYSA-N ethane-1,2-diol;hydrochloride Chemical compound Cl.OCCO OASOQJKCZXXDMI-UHFFFAOYSA-N 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
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- MBLBDJOUHNCFQT-LXGUWJNJSA-N aldehydo-N-acetyl-D-glucosamine Chemical compound CC(=O)N[C@@H](C=O)[C@@H](O)[C@H](O)[C@H](O)CO MBLBDJOUHNCFQT-LXGUWJNJSA-N 0.000 description 21
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 5
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- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 4
- 229930091371 Fructose Natural products 0.000 description 4
- 239000005715 Fructose Substances 0.000 description 4
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- QVYAWBLDJPTXHS-UHFFFAOYSA-N 5-hydroxyfuran-2-carbaldehyde Chemical compound OC1=CC=C(C=O)O1 QVYAWBLDJPTXHS-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
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- 235000021307 Triticum Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- 230000003260 anti-sepsis Effects 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
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- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
- C07D307/50—Preparation from natural products
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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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
- B01J37/02—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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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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
- B01J37/06—Washing
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
本发明涉及一种利用甲壳基固体酸催化剂制备糠醛的方法，以废弃甲壳为原料，通过酸处理或碱处理、沉淀、浸渍、焙烧，制备甲壳基固体酸催化剂；然后将含有半纤维素的生物质粉碎至60‑80目后置于反应釜中，加入质量分数为生物质粉末0.3‑3.6%的甲壳基固体酸催化剂，加入体积比为100:0‑50:50的水与氯化胆碱‑乙二醇，于160‑180°C下反应5 min‑1 h；反应结束后，冷却、过滤，滤渣为甲壳基固体酸催化剂，回用6次后，无明显失活，滤液含有糠醛，产率高达60%以上。本发明利用废弃甲壳制备的甲壳基固体酸催化剂，可有效催化生物质中的半纤维素转化为糠醛，糠醛的产率可提升至60%以上。并且易于回收和重复使用，解决了传统液态无机酸难于分离、回收的缺点，降低了后续提取废液的处理成本。The present invention relates to a method for preparing furfural by utilizing a crustacean-based solid acid catalyst. Using waste crustaceans as a raw material, the crustacean-based solid acid catalyst is prepared by acid treatment or alkali treatment, precipitation, impregnation and roasting; After the material is crushed to 60-80 mesh, it is placed in a reaction kettle, a chitosan-based solid acid catalyst whose mass fraction is 0.3-3.6% of biomass powder is added, and water and choline chloride are added in a volume ratio of 100:0-50:50. Ethylene glycol was reacted at 160-180 ° C for 5 min-1 h; after the reaction, cooling and filtering, the filter residue was a chitosan-based solid acid catalyst, and after being reused 6 times, there was no obvious inactivation, and the filtrate contained furfural, The yield is as high as 60% or more. The shell-based solid acid catalyst prepared by using the waste shell can effectively catalyze the conversion of hemicellulose in biomass into furfural, and the yield of furfural can be increased to more than 60%. Moreover, it is easy to recover and reuse, solves the disadvantage that the traditional liquid inorganic acid is difficult to separate and recover, and reduces the processing cost of the subsequent extraction waste liquid.
Description
Technical Field
The invention belongs to the technical field of solid acid catalysis, and particularly relates to a method for preparing biomass-based solid acid by using waste carapace and converting hemicellulose in biomass into furfural by a one-step method.
Background
Furfural is one of furan ring system derivatives, is an aromatic aldehyde, has active chemical properties, and can be used for preparing a plurality of derivatives through oxidation, reduction, condensation and other reactions, so that the furfural is widely applied to the fields of synthetic plastics, medicines, pesticides, spices, antisepsis, foods and the like. The industrial production of furfural mainly uses biomass rich in hemicellulose as a raw material, the hemicellulose is mainly a polymer mainly composed of pentose, the hemicellulose is hydrolyzed into xylose by homogeneous acid catalysis, and furfural is obtained by further dehydration, and the reaction formula is shown in fig. 13.
The biomass raw materials for producing furfural are abundant, and the large-quantity and cheap agricultural and forestry wastes such as bagasse, corncobs and straws can be used as the raw materials. The acid catalyst is an important factor for converting hemicellulose in the biomass into furfural and influencing the furfural yield. At present, liquid inorganic acids such as sulfuric acid, hydrochloric acid and the like are mainly adopted as acid catalysts for industrially producing furfural, the yield is generally low (30-50%), a large amount of waste residues, high-content COD waste liquid and SO2 waste gas are generated to cause serious environmental pollution, and the liquid acids are difficult to recycle.
The solid acid has the advantages of safety, small corrosivity, easy separation and recovery from a system, recycling and the like, has great application potential in the aspect of a novel environment-friendly production process, and has the tendency of gradually replacing the traditional liquid acid catalyst. The development of a solid acid catalyst which is rich in resources, low in price and high in efficiency is a hot point of attention. The existing solid acid catalysts such as transition metal oxides, ion exchange resins, molecular sieves and the like are usually utilized as non-renewable raw materials. Liujiafeng et al reviewed the reaction mechanism of catalytic furfural production from biomass and xylose as raw materials and the research progress of furfural production using different solid acid catalysts and reaction solvent systems in the article "influence of solid acid and two-phase reaction system on furfural production" ("New energy Advance" 2018(006) 003). Solid acids mentioned are molecular sieves, carbon-based solid acids, such as ZSM-5, H-beta zeolite, metal solid acids, resins, carbon-based solid acids, such as benzenesulfonic acid graphene oxide.
Waste crustae is an important biomass including shrimp shells, crab shells and the like, and the worldwide production amount is about 800 ten thousand tons each year. Disposal of waste crustae as a by-product of fishery aquaculture is also a currently outstanding problem. The crust mainly comprises chitin, protein, calcium and the like, has a certain biological and chemical structure, and can be prepared into an excellent solid acid catalyst through proper processing. In the fine chemical industry (08 th 2019), in the text of 'synthesis of 5-hydroxymethylfurfural by catalyzing fructose with chitosan-based solid acid', such as Yansha, chitosan is used as a raw material, a one-step hydrothermal carbonization and sulfonation method is adopted to synthesize a chitosan-based solid acid material (CASA), the chitosan-based solid acid material is used for catalyzing dehydration of fructose to synthesize 5-hydroxymethylfurfural (5-HMF) under the solvent-free condition, the influence of the dosage of a catalyst, the reaction temperature, the reaction time and the recycling frequency of the catalyst on the dehydration reaction is examined, and the catalytic performance of the chitosan-based solid acid material is compared with that of a chitin-based solid acid material (CISA). The result shows that the CASA material contains a large number of surface strong acid sites, so that the catalytic performance of the CASA material is more outstanding than that of the CISA material; when m (fructose) is 6: 1 and m (CASA) is reacted at 120 ℃ for 5 hours, the yield of 5-HMF is up to 63.2 percent, and CASA can be repeatedly used for 4 times without obvious inactivation. However, the study was directed to the production of 5-hydroxyfurfural using fructose. The invention patent application with the application number of CN201510631597.4, applied by Tianjin university of industry, discloses a method for preparing 5-hydroxymethylfurfural by degrading chitosan/chitin under the catalysis of solid acid, which comprises the following steps: the method comprises the steps of taking chitosan/chitin as a raw material, respectively taking a mixed solution of pure water and water/dimethyl sulfoxide as a reaction medium, adding a certain amount of catalyst, reacting for a period of time at constant temperature in a hydrothermal reaction kettle, and preparing 5-hydroxymethylfurfural, wherein the catalyst is solid acid and is used for heterogeneous catalytic conversion of chitosan/chitin in a system.
However, no report is available on the preparation of solid acid from waste carapace as a raw material and the application of the solid acid in catalyzing biomass to produce furfural.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing furfural by using a shell solid acid catalyst, a method for preparing a solid acid catalyst by using renewable resource waste shells and using the solid acid catalyst for catalyzing biomass to produce furfural, which solves the problem of treatment of the waste shells, and has the advantages of simple process, easy control and high furfural yield.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a method for preparing furfural by using a chitin solid acid catalyst comprises the following steps:
firstly, preparing a chitin solid acid catalyst by using waste carapace, wherein the solid acid catalyst is prepared by using the waste carapace as a raw material through acid treatment or alkali treatment, precipitation, impregnation and roasting, and specifically comprises the following steps:
(1) crushing the waste carapace, performing acid treatment or alkali treatment, washing to neutrality and drying;
(2) adding the processed carapace into a stannic chloride ethanol solution for full mixing, adjusting the pH value with ammonia water to generate a precipitate, separating and drying the precipitate; the concentration of the stannic chloride ethanol solution is 2.5 mg/mL;
(3) and (3) soaking the dried precipitate in a sulfuric acid solution, filtering and drying, and then putting the precipitate into a muffle furnace to be roasted at high temperature to obtain a solid, namely the chitin solid acid catalyst.
Step two: converting biomass containing hemicellulose by using a chitin solid acid catalyst one-step method to prepare furfural, and comprising the following steps:
(1) crushing biomass containing hemicellulose to 60-80 meshes, placing the biomass in a reaction kettle, adding a chitosan solid acid catalyst with the mass fraction of 0.3-3.6% of biomass powder, adding choline chloride-ethylene glycol and water with the volume ratio of 0:100-40:60 (not taking 0 point), and reacting for 5min-1h at 160-180 ℃.
The biomass containing hemicellulose is crop straws such as corn straws, wheat straws and the like.
After alkali treatment is carried out on the crushed waste carapace, when the volume ratio of choline chloride-glycol to water is 10:90, the yield of furfural is the maximum; and the yield of the furfural is the maximum when the volume ratio of choline chloride-ethylene glycol to water is 20:80 after the crushed waste crusta is subjected to acid treatment.
(2) After the reaction is finished, cooling and filtering, wherein the filter residue is a chitin solid acid catalyst, the filtrate is analyzed by HPLC, and the filter residue obtained after filtering can be directly recycled or separated, washed by water, dried and stored for later use.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) the invention utilizes the shell solid acid catalyst prepared by waste shells to effectively catalyze the conversion of hemicellulose in biomass into furfural, and the yield of furfural can be improved to more than 60%. And the method is easy to recycle and reuse, solves the defect that the traditional liquid inorganic acid is difficult to separate and recycle, and reduces the treatment cost of the subsequent extraction waste liquid.
(2) The invention takes the waste carapace as the raw material to prepare the carapace solid acid catalyst, has rich and reproducible raw material sources, simple process and easy mass production, and reduces the energy consumption and pollution of the production.
(3) The chitin solid acid catalyst is repeatedly used for 6 times without obvious inactivation. The replacement frequency of the solid acid catalyst is reduced, and the production cost is reduced.
Drawings
FIG. 1 is a FT-IR diagram of the spent alkali-treated crustae of the present invention (a) and a solid acid catalyst prepared from the spent alkali-treated crustae (b);
FIG. 2 is an XRD pattern of the spent alkali-treated crustae of the present invention (a) and a solid acid catalyst prepared from the spent alkali-treated crustae (b);
FIG. 3 is a graph showing the effect of different volume ratios of choline chloride-ethylene glycol to water on furfural yield of a solid acid catalyst prepared by treating waste carapace with alkali in the present invention;
FIG. 4 is a graph showing the effect of different equivalent weights of solid acid catalyst prepared from alkali-treated waste carapace on furfural yield in accordance with the present invention;
FIG. 5 is a graph of the effect of different conversion temperatures on furfural yield of a solid acid catalyst prepared by treating waste carapace with alkali in accordance with the present invention;
FIG. 6 is a graph showing the effect of the number of times the solid acid catalyst prepared by treating waste crustaceans with alkali has been used on the furfural yield in accordance with the present invention;
FIG. 7 is a FT-IR diagram of the acid treated waste crustacean (a) and the solid acid catalyst prepared from the acid treated waste crustacean (b) of the present invention;
FIG. 8 is an XRD pattern of the acid treated waste crustae of the present invention (a) and a solid acid catalyst prepared from the acid treated waste crustae (b);
FIG. 9 is a graph of the effect of different volume ratios of choline chloride-ethylene glycol to water on furfural yield of the solid acid catalyst prepared from acid treatment of waste crustaceans in the present invention;
FIG. 10 is a graph showing the effect of different equivalent weights of solid acid catalyst prepared from acid treatment of waste crustae on furfural yield in accordance with the present invention;
FIG. 11 is a graph of the effect of different conversion temperatures on furfural yield of a solid acid catalyst prepared by acid treatment of waste crustaceans in accordance with the present invention;
FIG. 12 is a graph showing the effect of the number of times the solid acid catalyst is used to prepare acid crust on the furfural yield in the present invention;
fig. 13 is a flow chart of the conventional furfural industrial production.
Detailed Description
The present invention will be further described with reference to specific examples for the purpose of understanding the present invention. It should be understood by those skilled in the art that the examples are only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention. In the field of the invention, the following description of the invention can be made based on different forms of changes and modifications, all of which are within the spirit and principle of the invention, and all changes, equivalents and improvements made within the scope of the invention are included in the claims.
Example 1: preparation of chitin solid acid catalyst by using waste chitin
(1) Alkali treatment of the waste shrimp shells: crushing the waste shrimp shell powder to 60-200 meshes, soaking 50g of the shrimp shell powder in 300mL of 1M sodium hydroxide solution, and stirring at room temperature for 3 h. Filtering the alkali-treated shrimp shell powder, washing with water to neutrality, putting into a 70 ℃ oven, and drying to obtain the alkali-treated shrimp shell. The alkali-treated shrimp shells are characterized by FT-IR and XRD, the FT-IR pattern is shown in figure 1a, and the XRD pattern is shown in figure 2 a.
(2) Taking 4.2g of alkali-treated shrimp shell and adding 1.94g of SnCl4·5H2O80 mL of ethanol (concentration 2.5mg/mL) was thoroughly stirred, then the pH of the solution was adjusted to 6 with 25% aqueous ammonia, and the resulting colloidal solution was placed in an oven at 70 ℃ and dried for 48 hours, and then dried at 90 ℃ for 48 hours to obtain a solid powder.
(3) And 4g of the obtained solid powder is taken and soaked in 60mL of 0.5M sulfuric acid, the solid powder is filtered after 3h, the filter cake is dried for 12h at the temperature of 90 ℃, and then the filter cake is placed in a muffle furnace for roasting at the temperature of 550 ℃ for 4h, so that the solid acid catalyst prepared based on the alkali-treated shrimp shell is obtained. The alkali-treated shrimp shell solid acid catalyst is characterized by FT-IR and XRD, the FT-IR figure is shown in figure 1b, and the XRD figure is shown in figure 2 b.
Example 2: preparation of furfural by using corn straw as chitin solid acid catalyst
(1) Drying corn stalk at 70 deg.C to constant weight, and pulverizing to 60-80 mesh.
(2) Weighing 3g of corn straw powder, placing the corn straw powder in a 100mL reaction kettle, adding 40mL of choline chloride-ethylene glycol (a deep eutectic solvent synthesized by choline chloride and ethylene glycol and purchased from Shanghai Chengjie chemical Co., Ltd.), water (0:100-40:60, v: v) and the alkali-treated shrimp shell solid acid catalyst (0-3.6 wt%) obtained in example 1, magnetically stirring at 500rpm, and reacting at 180 ℃ for 5-60 min. After the reaction is finished, cooling to room temperature by water cooling, and opening the reaction kettle. And filtering and separating solid and liquid, wherein the solid is a catalyst, and the liquid is a reaction liquid containing furfural. The furfural content was determined by high performance liquid chromatography. The solid acid catalyst can be directly recycled, or after separation, washed with water, dried and stored for later use. As shown in fig. 6, the furfural yield decreased by 12.2% after 6 times of reuse of the solid acid catalyst.
(3) Technological parameter investigation:
(a) when the volume ratio of choline chloride-ethylene glycol to water is adjusted, the yield change of the conversion of hemicellulose in the corn straw into furfural by the solid acid is shown in fig. 3, and it can be seen that when the volume ratio of choline chloride-ethylene glycol to water is 10:90, the yield of furfural is the maximum and is 52.4%.
(b) When the equivalent of the solid acid catalyst for alkali treatment of the shrimp shells is adjusted, the yield change condition of converting hemicellulose in the corn straws into furfural by solid acid catalysis is shown in fig. 4, and it can be known that the yield of furfural is the maximum when the equivalent of the solid acid catalyst for alkali treatment of the shrimp shells is 0.6 wt%.
(c) When the reaction temperature is adjusted, the yield change condition of the conversion of hemicellulose in the corn straws into furfural by solid acid catalysis is shown in fig. 5, and it can be known that the yield of furfural is the maximum when the temperature is 170 ℃ and the reaction is carried out for 30 min.
Example 3: preparation of chitin solid acid catalyst by using waste chitin
(1) Acid treatment of waste shrimp shells: crushing the waste shrimp shell powder to 60-200 meshes, soaking 50g of the shrimp shell powder in 300mL of 0.5M sulfuric acid solution, and stirring at room temperature for 3 hours. Filtering the acid-treated shrimp shell powder, washing the shrimp shell powder with water to be neutral, putting the shrimp shell powder into a 70 ℃ oven, and drying the shrimp shell powder for 24 hours to obtain the acid-treated shrimp shell. The acid treated shrimp shells were characterized by FT-IR and XRD, with the FT-IR pattern shown in FIG. 7a and the XRD pattern shown in FIG. 8 a.
(2) 4.2g of acid-treated shrimp shell was placed in a container containing 1.94g of SnCl4·5H2Stirring O80 mL of ethanol fully, then adjusting the pH value of the solution to 6 by using 25% ammonia water, placing the colloidal solution in a 70 ℃ oven, drying for 48h, and then drying for 48h at 90 ℃ to obtain solid powder.
(3) And 4g of the obtained solid powder is taken and soaked in 60mL of 0.5M sulfuric acid, the filtration is carried out after 3h, the filter cake is dried for 12h at the temperature of 90 ℃, and then the filter cake is placed in a muffle furnace for roasting at the temperature of 550 ℃ for 4h, so that the solid acid catalyst prepared based on the acid-treated shrimp shell is obtained. The acid-treated shrimp shell solid acid catalyst is characterized by FT-IR and XRD, the FT-IR figure is shown in figure 7b, and the XRD figure is shown in figure 8 b.
Example 4: preparation of furfural by using corn straw as chitin solid acid catalyst
(1) Drying corn stalk at 70 deg.C to constant weight, and pulverizing to 60-80 mesh.
(2) Weighing 3g of corn straw powder, placing the corn straw powder into a 100mL reaction kettle, adding 40mL of choline chloride-ethylene glycol and water (0:100-50:50, v: v) and the acid-treated shrimp shell solid acid catalyst (0-3.6 wt%) obtained in example 3, magnetically stirring at 500rpm, and reacting at 180 ℃ for 5-60 min. After the reaction is finished, cooling to room temperature by water cooling, and opening the reaction kettle. And filtering and separating solid and liquid, wherein the solid is a catalyst, and the liquid is a reaction liquid containing furfural. The furfural content was determined by high performance liquid chromatography. The solid acid catalyst can be directly recycled, or after separation, washed with water, dried and stored for later use. As shown in fig. 12, the solid acid catalyst was reused in example 4, and furfural yield decreased by 13.6% after 6 times of reuse.
(3) Technological parameter investigation:
(a) when the volume ratio of choline chloride-ethylene glycol to water is adjusted, the yield change condition of the solid acid catalysis of the conversion of hemicellulose in the corn stalks into furfural is shown in fig. 9, and it can be known that when the volume ratio of choline chloride-ethylene glycol to water is 20:80, the yield of furfural is the maximum and is 62.3%.
(b) When the equivalent of the acid-treated shrimp shell solid acid catalyst is adjusted, the yield of the furfural obtained by converting hemicellulose in the corn straw into the furfural through the solid acid catalysis is changed as shown in fig. 10, and it can be seen that the yield of the furfural is the largest when the equivalent of the acid-treated shrimp shell solid acid catalyst is 0.6 wt%.
(c) When the reaction temperature is adjusted, the yield change condition of the conversion of hemicellulose in the corn straws into furfural by solid acid catalysis is shown in fig. 11, and it can be known that the yield of furfural is the maximum when the temperature is 170 ℃ and the reaction time is 20 min.
The above description is only an example of the present invention and is not intended to limit the scope of the present invention, and all methods described in the present specification or other related fields directly or indirectly can be used in the present invention.
Claims (6)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116082279A (en) * | 2022-12-30 | 2023-05-09 | 浙江大学 | A method and device for the co-production of furfural and levulinic acid by dilute acid hydrolysis coupled with solid acid catalytic conversion of biomass |
| CN116459849A (en) * | 2023-04-06 | 2023-07-21 | 常州大学 | Preparation method and application of biological-based hydroxyapatite solid acid catalyst |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005226045A (en) * | 2004-02-16 | 2005-08-25 | Nippon Shokubai Co Ltd | Dispersion of inorganic fine particles |
| CN101691526A (en) * | 2009-09-30 | 2010-04-07 | 华中农业大学 | Method for preparing biodiesel by using biological carapace solid base catalyst |
| CN102824920A (en) * | 2012-09-27 | 2012-12-19 | 唐山师范学院 | Method for preparing furfural solid-acid catalyst through utilizing corn stalks |
| US20130023679A1 (en) * | 2011-07-21 | 2013-01-24 | Industrial Technology Research Institute | Preparation of furfural compounds, and mixture for preparing the same |
| CN103242270A (en) * | 2013-05-28 | 2013-08-14 | 华东理工大学 | Method for preparing furfural compounds from biomass |
| CN105153080A (en) * | 2015-09-28 | 2015-12-16 | 天津工业大学 | Method for preparing 5-hydroxymethyl furfural by degrading solid acid catalysis chitosan/chitin |
| CN105254600A (en) * | 2015-09-28 | 2016-01-20 | 天津工业大学 | Degradation of chitosan/chitin with sulfonated carbon solid acid into high value 5-hydroxymethyl furfural |
| CN106111188A (en) * | 2016-06-20 | 2016-11-16 | 大连理工大学 | The preparation method of a kind of biological carbon based solid acid and the application in cellulose hydrolysis |
| WO2017032926A2 (en) * | 2015-08-27 | 2017-03-02 | Teknologian Tutkimuskeskus Vtt Oy | Process for converting biomass |
| CN106732673A (en) * | 2016-11-10 | 2017-05-31 | 常州大学 | A kind of construction method of the solid acid catalyst with montmorillonite as carrier |
| CN107199043A (en) * | 2016-03-18 | 2017-09-26 | 中国石油化工股份有限公司 | Solid acid catalyst and its preparation method and application and the method for preparing Furnan products |
| CN108325515A (en) * | 2018-01-31 | 2018-07-27 | 华南理工大学 | A kind of porous carbon-based solid acid catalyst of tin supported and the preparation method and application thereof |
| CN108940373A (en) * | 2018-07-16 | 2018-12-07 | 广东石油化工学院 | Based on shrimp, the organic reaction catalyst of crab waste and the preparation method and application thereof |
| CN110317156A (en) * | 2019-08-13 | 2019-10-11 | 广东海洋大学 | A kind of method that depth eutectic solvent microemulsion extracts system and extracts astaxanthin |
| CN110944761A (en) * | 2017-05-30 | 2020-03-31 | 新加坡国立大学 | Crustacean Waste Treatment Methods |
| WO2020245288A1 (en) * | 2019-06-06 | 2020-12-10 | Purac Biochem B.V. | Process for manufacturing hydroxymethylfurfural |
| CN113318785A (en) * | 2021-04-20 | 2021-08-31 | 常州大学 | Shrimp shell/metal organic framework polymer type biomass composite catalyst and preparation method and application thereof |
-
2021
- 2021-09-10 CN CN202111060817.4A patent/CN113788806A/en active Pending
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005226045A (en) * | 2004-02-16 | 2005-08-25 | Nippon Shokubai Co Ltd | Dispersion of inorganic fine particles |
| CN101691526A (en) * | 2009-09-30 | 2010-04-07 | 华中农业大学 | Method for preparing biodiesel by using biological carapace solid base catalyst |
| US20130023679A1 (en) * | 2011-07-21 | 2013-01-24 | Industrial Technology Research Institute | Preparation of furfural compounds, and mixture for preparing the same |
| CN102824920A (en) * | 2012-09-27 | 2012-12-19 | 唐山师范学院 | Method for preparing furfural solid-acid catalyst through utilizing corn stalks |
| CN103242270A (en) * | 2013-05-28 | 2013-08-14 | 华东理工大学 | Method for preparing furfural compounds from biomass |
| WO2017032926A2 (en) * | 2015-08-27 | 2017-03-02 | Teknologian Tutkimuskeskus Vtt Oy | Process for converting biomass |
| CN105254600A (en) * | 2015-09-28 | 2016-01-20 | 天津工业大学 | Degradation of chitosan/chitin with sulfonated carbon solid acid into high value 5-hydroxymethyl furfural |
| CN105153080A (en) * | 2015-09-28 | 2015-12-16 | 天津工业大学 | Method for preparing 5-hydroxymethyl furfural by degrading solid acid catalysis chitosan/chitin |
| CN107199043A (en) * | 2016-03-18 | 2017-09-26 | 中国石油化工股份有限公司 | Solid acid catalyst and its preparation method and application and the method for preparing Furnan products |
| CN106111188A (en) * | 2016-06-20 | 2016-11-16 | 大连理工大学 | The preparation method of a kind of biological carbon based solid acid and the application in cellulose hydrolysis |
| CN106732673A (en) * | 2016-11-10 | 2017-05-31 | 常州大学 | A kind of construction method of the solid acid catalyst with montmorillonite as carrier |
| CN110944761A (en) * | 2017-05-30 | 2020-03-31 | 新加坡国立大学 | Crustacean Waste Treatment Methods |
| CN108325515A (en) * | 2018-01-31 | 2018-07-27 | 华南理工大学 | A kind of porous carbon-based solid acid catalyst of tin supported and the preparation method and application thereof |
| CN108940373A (en) * | 2018-07-16 | 2018-12-07 | 广东石油化工学院 | Based on shrimp, the organic reaction catalyst of crab waste and the preparation method and application thereof |
| WO2020245288A1 (en) * | 2019-06-06 | 2020-12-10 | Purac Biochem B.V. | Process for manufacturing hydroxymethylfurfural |
| CN110317156A (en) * | 2019-08-13 | 2019-10-11 | 广东海洋大学 | A kind of method that depth eutectic solvent microemulsion extracts system and extracts astaxanthin |
| CN113318785A (en) * | 2021-04-20 | 2021-08-31 | 常州大学 | Shrimp shell/metal organic framework polymer type biomass composite catalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张明川;臧洪俊;余松柏;颜丙;蒋奕;谢瑞瑞;: "甲壳素生物质转化为高附加值化合物研究进展", 化工进展, no. 03 * |
| 臧洪俊;焦硕磊;李明广;安国栋;张明川;王娇;: "硅胶固载化酸性离子液体催化壳聚糖生物质制备5-羟甲基糠醛", 天津工业大学学报, no. 04 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116082279A (en) * | 2022-12-30 | 2023-05-09 | 浙江大学 | A method and device for the co-production of furfural and levulinic acid by dilute acid hydrolysis coupled with solid acid catalytic conversion of biomass |
| CN116459849A (en) * | 2023-04-06 | 2023-07-21 | 常州大学 | Preparation method and application of biological-based hydroxyapatite solid acid catalyst |
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