CN115301284A - Modified Beta molecular sieve for catalytically converting biomass into lactic acid and preparation method and application thereof - Google Patents
Modified Beta molecular sieve for catalytically converting biomass into lactic acid and preparation method and application thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 110
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 110
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 235000014655 lactic acid Nutrition 0.000 title claims abstract description 38
- 239000004310 lactic acid Substances 0.000 title claims abstract description 38
- 239000002028 Biomass Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 87
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- -1 rare earth metal salt Chemical class 0.000 claims abstract description 36
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 150000001225 Ytterbium Chemical class 0.000 claims abstract description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical group [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 14
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 12
- 239000008103 glucose Substances 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 8
- 229930006000 Sucrose Natural products 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- 229930091371 Fructose Natural products 0.000 claims description 4
- 239000005715 Fructose Substances 0.000 claims 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 claims description 4
- 150000001720 carbohydrates Chemical class 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002910 rare earth metals Chemical group 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000001994 activation Methods 0.000 abstract description 7
- 230000004913 activation Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 43
- 238000005119 centrifugation Methods 0.000 description 30
- 229910001220 stainless steel Inorganic materials 0.000 description 19
- 239000010935 stainless steel Substances 0.000 description 19
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 description 18
- 239000007791 liquid phase Substances 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 238000004128 high performance liquid chromatography Methods 0.000 description 15
- 238000005303 weighing Methods 0.000 description 15
- 230000007935 neutral effect Effects 0.000 description 13
- 239000006228 supernatant Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 11
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 7
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 4
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000000855 fermentation Methods 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- ALJCLXGXZFZGEM-UHFFFAOYSA-K ytterbium(3+);triacetate;tetrahydrate Chemical compound O.O.O.O.[Yb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O ALJCLXGXZFZGEM-UHFFFAOYSA-K 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- OSCVBYCJUSOYPN-UHFFFAOYSA-K ytterbium(3+);triacetate Chemical compound [Yb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OSCVBYCJUSOYPN-UHFFFAOYSA-K 0.000 description 1
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
-
- 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
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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Abstract
The invention discloses a modified Beta molecular sieve for catalytically converting biomass into lactic acid, and a preparation method and application thereof. Mixing a certain amount of Beta molecular sieve with concentrated nitric acid, then carrying out dealumination, carrying out solid-liquid separation after reaction, rinsing for multiple times, and drying to obtain the dealuminated Beta molecular sieve; uniformly mixing a certain amount of rare earth metal salt and the dealuminized Beta molecular sieve, grinding, and roasting to obtain the modified Beta molecular sieve, wherein the rare earth metal salt is yttrium salt or ytterbium salt. The novel modified Beta molecular sieve catalyst developed by the invention has simple preparation process and more excellent catalytic performance, and can be recycled after roasting and activation; meanwhile, in the catalytic reaction, the reaction raw materials are cheap and easy to obtain, the reaction conditions are simple and the reaction time is short.
Description
Technical Field
The invention relates to the technical field of catalytic conversion of biomass into lactic acid, in particular to a modified Beta molecular sieve for catalytic conversion of biomass into lactic acid and a preparation method and application thereof.
Background
Along with the continuous consumption of fossil energy, world resources are increasingly deficient, the environment is gradually worsened, and meanwhile, the shortage of fossil energy also makes the development of clean renewable energy receive more and more attention. The biomass energy is regarded as the most potential disposable energy source for replacing energy sources due to the advantages of wide distribution, low price, environmental friendliness, sustainable utilization and the like, and has practical significance for producing chemical products with high added values by utilizing the biomass.
Lactic acid is an important platform molecular compound, has wide application in various industries such as chemical industry, medicine, food and the like, and is also applied to the production of degradable plastics in recent years, so that the yield of the lactic acid has a huge gap. At present, the industrial production of lactic acid mainly adopts a microbial fermentation method, but the fermentation method has the defects of low overall utilization rate, complicated fermentation production process, long production period, unsatisfactory yield and purity of the obtained product and the like. Therefore, people aim at the catalytic method which is simple and rapid in reaction.
Since Beta molecular sieves are synthesized, excellent catalytic performance is shown when the Beta molecular sieves are applied to the field of catalytic conversion of biomass, but at present, the mainstream modified Beta molecular sieves mostly use Sn as a main catalytic element, and have certain narrowness in research depth, so that the research significance is realized by finding a new catalytic effect which can replace or even exceed Sn.
Disclosure of Invention
The invention aims to develop a novel modified Beta molecular sieve for catalyzing biomass to produce lactic acid, which can break through the current situation that Sn is the main element and further improve the yield of lactic acid.
In order to achieve the above object, the present invention provides a method for preparing a modified Beta molecular sieve for catalytically converting biomass into lactic acid, the method comprising the steps of:
mixing a certain amount of Beta molecular sieve with concentrated nitric acid, dealuminizing, carrying out solid-liquid separation after reaction, rinsing for multiple times, and drying to obtain the dealuminized Beta molecular sieve; uniformly mixing a certain amount of rare earth metal salt and the dealuminized Beta molecular sieve, grinding, and roasting to obtain the modified Beta molecular sieve, wherein the rare earth metal salt is yttrium salt or ytterbium salt.
In one embodiment of the invention, the ratio of the Beta molecular sieve to the concentrated nitric acid is 10-25g of Beta molecular sieve and 200-500mL of concentrated nitric acid.
In one embodiment of the invention, the dealumination is carried out at 90-120 ℃ for 18-24 h.
In one embodiment of the invention, the concentration of the concentrated nitric acid is 65% to 68%.
In one embodiment of the present invention, the rare earth metal salt is preferably a rare earth metal acetate or a rare earth metal acetate hydrate, wherein the ratio of the rare earth metal acetate or the rare earth metal acetate hydrate to the dealuminized Beta molecular sieve is 1g dealuminized Beta molecular sieve and 0.4-1.6mmol of rare earth metal acetate/rare earth metal acetate hydrate (based on the molar amount of metal atoms).
In one embodiment of the invention, after dealuminization centrifugation, the supernatant is rinsed for a plurality of times until the supernatant is neutral, wherein the neutral refers to the pH value of 6.5-7.5.
In one embodiment of the invention, the drying is at 90-130 ℃ for 8-16h.
In one embodiment of the invention, the grinding time is 20-40min.
In one embodiment of the present invention, the calcination condition is calcination at 500 to 550 ℃ for 5 to 7 hours.
The invention also provides the modified Beta molecular sieve catalyst prepared by the preparation method.
The invention also provides a method for catalytically converting biomass into lactic acid, which comprises the following steps: adding a quantitative reaction substrate, the modified Beta molecular sieve catalyst and water into a reaction kettle for reaction, wherein the reaction substrate is added according to the following proportion: 135-250mg of reaction substrate, 100-180mg of catalyst and 10-15 mL of water.
In one embodiment of the invention, the reaction substrate is a saccharide.
In one embodiment of the present invention, the saccharide is selected from glucose, sucrose and fructose.
In one embodiment of the invention, the reaction is carried out in a rotary oven, preferably at a speed of 10 to 30r/min.
In one embodiment of the invention, the reaction temperature is 160-230 ℃, and the reaction time is 1-6 h.
In one embodiment of the invention, the catalyst can be activated and recycled for reuse after the reaction.
In one embodiment of the invention, lactic acid is separated after the reaction is finished, and the lactic acid separation method is centrifugation for 3-6min at 4000-6000 r/min.
In one embodiment of the invention, the catalyst activation process is to bake in an air atmosphere at 500-550 ℃ for 5-7h after fully rinsing with alcohol.
The invention has the following beneficial effects:
compared with the catalyst on the market, the novel modified Beta molecular sieve catalyst developed by the invention has the advantages of simple preparation process, more excellent catalytic performance and reutilization after roasting and activation; meanwhile, in the catalytic reaction, the reaction raw materials are cheap and easy to obtain, the reaction conditions are simple and the reaction time is short.
Drawings
FIG. 1 is a liquid chromatogram of the liquid phase product after catalysis of the Y-Beta molecular sieve in example 1.
FIG. 2 is a representation of XRD of different types of Beta molecular sieves in examples and comparative examples of the present invention.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings.
Commercial grade Beta molecular sieves were purchased from southern university catalyst works (silica to alumina ratio of 25).
The product yield in the invention is calculated by carbon mole number, and the calculation formula is as follows:
example 1
Preparing a catalyst: mixing a commercial grade Beta molecular sieve with concentrated nitric acid (the purity is 65% -68%) according to the proportion of mixing 25g of the Beta molecular sieve with 500mL of the concentrated nitric acid, stirring and reacting for 20h at 100 ℃ for dealuminization, centrifuging after the reaction, rinsing for many times until the supernatant is neutral, and then drying for 16h at 90 ℃ to obtain the dealuminized Beta molecular sieve; 1g of dealuminized Beta molecular sieve and 308.4mg of yttrium acetate (1.2 mmol Y) are mixed and ground for 30min, and then the mixture is roasted at the high temperature of 550 ℃ for 6h to obtain the aluminum-free Y-Beta molecular sieve catalyst.
And (3) catalytic reaction: weighing 225mg of glucose, 160mg of aluminum-free Y-Beta molecular sieve catalyst and 10mL of deionized water, adding into a polytetrafluoroethylene lining with the capacity of 50mL, placing in a stainless steel reaction kettle, and then sending to a rotary oven for reaction, wherein the rotating speed of the rotary oven is set to be 20r/min, the temperature is 190 ℃, and the reaction is carried out for 3 hours; the product is obtained by centrifugation, the centrifugation rate is 4000r/min, the time is 4min, the yield of the target product lactic acid is 45.2 percent and the yield of the main byproduct 5-hydroxymethylfurfural is only 10.5 percent by analyzing the liquid phase product by adopting High Performance Liquid Chromatography (HPLC).
The liquid chromatogram of the liquid phase product in the reaction system is shown in figure 1, the lactic acid peaks at a retention time of about 13min, and the XRD characterization of the aluminum-free Y-Beta molecular sieve catalyst is shown in figure 2.
Example 2
Preparing a catalyst: mixing a commercial grade Beta molecular sieve with concentrated nitric acid (the purity is 65% -68%) according to the proportion of mixing 25g of the Beta molecular sieve with 500mL of the concentrated nitric acid, stirring and reacting for 20h at 100 ℃ for dealuminization, centrifuging after the reaction, rinsing for many times until the supernatant is neutral, and then drying for 16h at 90 ℃ to obtain the dealuminized Beta molecular sieve; 1g of dealuminized Beta molecular sieve and 506.4mg of ytterbium acetate tetrahydrate (1.2 mmol of Yb) are mixed and ground for 30min, and then the mixture is roasted at the high temperature of 550 ℃ for 6h to obtain the aluminum-free Y-Beta molecular sieve catalyst.
And (3) catalytic reaction: weighing 225mg of glucose, 160mg of aluminum-free Yb-Beta molecular sieve catalyst and 10mL of deionized water, adding into a polytetrafluoroethylene lining with the capacity of 50mL, placing in a stainless steel reaction kettle, and then placing in a rotary oven for reaction, wherein the rotating speed of the rotary oven is set to be 20r/min, the temperature is 190 ℃, and reacting for 3h; the product is obtained by centrifugation, the centrifugation rate is 4000r/min, the time is 4min, the yield of the target product lactic acid is 43.2 percent and the yield of the main byproduct 5-hydroxymethylfurfural is only 8.8 percent by analyzing the liquid phase product by adopting High Performance Liquid Chromatography (HPLC).
Example 3
Preparing a catalyst: mixing commercial grade Beta molecular sieve and concentrated nitric acid (the purity is 65% -68%) according to the proportion of 25g Beta molecular sieve and 500mL concentrated nitric acid, stirring and reacting for 20h at 100 ℃ to perform dealumination, centrifuging after reaction, rinsing for many times until the supernatant is neutral, and then drying for 8h at 130 ℃ to obtain the dealuminated Beta molecular sieve; mixing 1g of dealuminized Beta molecular sieve and 257mg of yttrium acetate (1.0 mmol Y), grinding for 30min, and then roasting at the high temperature of 550 ℃ for 6h to obtain the aluminum-free Y-Beta molecular sieve catalyst.
And (3) catalytic reaction: weighing 225mg of sucrose, 140mg of aluminum-free Y-Beta molecular sieve catalyst and 10mL of deionized water, adding into a polytetrafluoroethylene lining with the capacity of 50mL, placing in a stainless steel reaction kettle, and then placing in a rotary oven for reaction, wherein the rotating speed of the rotary oven is set to be 20r/min, the temperature is set to be 210 ℃, and the reaction is carried out for 4 hours; the product is obtained by centrifugation, the centrifugation rate is 5000r/min, the time is 6min, and the High Performance Liquid Chromatography (HPLC) is adopted to analyze the liquid phase product, so that the yield of the lactic acid is 45.2 percent, and the yield of the main byproduct 5-hydroxymethylfurfural is only 11.4 percent.
Example 4
Preparing a catalyst: mixing commercial grade Beta molecular sieve and concentrated nitric acid (the purity is 65% -68%) according to the proportion of 25g Beta molecular sieve and 500mL concentrated nitric acid, stirring and reacting for 20h at 100 ℃ to perform dealumination, centrifuging after reaction, rinsing for many times until the supernatant is neutral, and then drying for 8h at 130 ℃ to obtain the dealuminated Beta molecular sieve; 1g of dealuminized Beta molecular sieve and 422.3mg of ytterbium acetate tetrahydrate (1.0 mmol of Yb) are mixed and ground for 30min, and then the mixture is roasted at the high temperature of 550 ℃ for 6h to obtain the aluminum-free Y-Beta molecular sieve catalyst.
And (3) catalytic reaction: weighing 225mg of sucrose, 140mg of aluminum-free Yb-Beta molecular sieve catalyst and 10mL of deionized water, adding into a polytetrafluoroethylene lining with the capacity of 50mL, placing in a stainless steel reaction kettle, and then sending to a rotary oven for reaction, wherein the rotating speed of the rotary oven is set to be 20r/min, the temperature is set to be 210 ℃, and the reaction is carried out for 4 hours; the product is obtained by centrifugation, the centrifugation rate is 5000r/min, the time is 6min, the High Performance Liquid Chromatography (HPLC) is adopted to analyze the liquid phase product, the yield of the lactic acid is 47.1 percent, and the yield of the main byproduct 5-hydroxymethylfurfural is only 12.3 percent. .
Example 5 illustrates catalyst recycle
The solid obtained after the reaction product in the example 1 is centrifuged is roasted for 6h at 550 ℃ for activation, and the catalyst which is recycled once is obtained.
And (3) catalytic reaction: weighing 225mg of glucose, 160mg of the recycled Y-Beta molecular sieve catalyst and 10mL of deionized water, adding the weighed materials into a polytetrafluoroethylene lining with the capacity of 50mL, placing the polytetrafluoroethylene lining into a stainless steel reaction kettle, and then putting the stainless steel reaction kettle into a rotary oven for reaction, wherein the rotating speed of the rotary oven is set to be 20r/min, the temperature is 190 ℃, and reacting for 3 hours; the product is obtained by centrifugation with a centrifugation rate of 4000r/min for 4min, and the yield of lactic acid is 43.5% by analyzing the liquid phase product by High Performance Liquid Chromatography (HPLC).
The catalyst is repeatedly recycled for reaction, and the yield of the lactic acid can still reach 38.6 percent after the second recycling.
Example 6 illustrates catalyst recycle
And (3) centrifuging the reaction product in the example 2, and roasting the obtained solid at 550 ℃ for 6h for activation to obtain the once-recycled catalyst.
And (3) catalytic reaction: weighing 225mg of glucose, 160mg of the once-recycled Yb-Beta molecular sieve catalyst and 10mL of deionized water, adding into a polytetrafluoroethylene inner liner with the capacity of 50mL, placing the inner liner in a stainless steel reaction kettle, and then putting the inner liner in a rotary oven for reaction, wherein the rotating speed of the rotary oven is set to be 20r/min, the temperature is 190 ℃, and reacting for 3 hours; the product is obtained by centrifugation with a centrifugation rate of 4000r/min for 4min, and the yield of lactic acid is 40.5% by analyzing the liquid phase product by High Performance Liquid Chromatography (HPLC).
The catalyst is repeatedly recycled for reaction, and the yield of the lactic acid can still reach 36.4 percent after the second recycling.
Example 7 illustrates catalyst recycle
The solid obtained after the reaction product in the example 3 is centrifuged is roasted for 6h at 550 ℃ for activation, and the catalyst which is recycled for one time is obtained.
And (3) catalytic reaction: weighing 225mg of sucrose, 140mg of the recycled Y-Beta molecular sieve catalyst and 10mL of deionized water, adding into a polytetrafluoroethylene lining with the capacity of 50mL, placing in a stainless steel reaction kettle, and then sending to a rotary oven for reaction, wherein the rotating speed of the rotary oven is set to be 20r/min, the temperature is set to be 210 ℃, and the reaction is carried out for 4 hours; the product was obtained by centrifugation at 5000r/min for 6min, and the yield of lactic acid was 42.3% by High Performance Liquid Chromatography (HPLC) analysis of the liquid product.
The catalyst is repeatedly recycled for reaction, and the yield of the lactic acid can still reach 38.2 percent after the second recycling.
Example 8 illustrates catalyst recycle
And (3) centrifuging the reaction product obtained in the example 4, and roasting the obtained solid at 550 ℃ for 6h for activation to obtain the once-recycled catalyst.
And (3) catalytic reaction: weighing 225mg of sucrose, 140mg of the once-recycled Yb-Beta molecular sieve catalyst and 10mL of deionized water, adding into a polytetrafluoroethylene lining with the capacity of 50mL, placing in a stainless steel reaction kettle, and then putting in a rotary oven for reaction, wherein the rotating speed of the rotary oven is set to be 20r/min, the temperature is 210 ℃, and reacting for 4h; the product was obtained by centrifugation at 5000r/min for 6min, and the yield of lactic acid was 45.8% by High Performance Liquid Chromatography (HPLC) analysis of the liquid phase product.
The catalyst is repeatedly recycled for reaction, and the yield of the lactic acid can still reach 38.6 percent after the second recycling.
Example 9
Preparing a catalyst: mixing commercial grade Beta molecular sieve and concentrated nitric acid (the purity is 65% -68%) according to the proportion of 25g Beta molecular sieve and 500mL concentrated nitric acid, stirring and reacting for 18h at 120 ℃ to perform dealumination, centrifuging after reaction, rinsing for many times until the supernatant is neutral, and then drying for 10h at 130 ℃ to obtain the dealuminated Beta molecular sieve; 1g of dealuminized Beta molecular sieve and 205.6mg of yttrium acetate (0.8 mmol Y) are mixed and ground for 40min, and then the mixture is roasted at the high temperature of 500 ℃ for 7h to obtain the aluminum-free Y-Beta molecular sieve catalyst.
And (3) catalytic reaction: weighing 160mg of fructose, 115mg of an aluminum-free Y-Beta molecular sieve catalyst and 10mL of deionized water, adding the weighed materials into a polytetrafluoroethylene lining with the capacity of 50mL, placing the polytetrafluoroethylene lining into a stainless steel reaction kettle, and then sending the stainless steel reaction kettle to a rotary oven for reaction, wherein the rotating speed of the rotary oven is set to be 20r/min, the temperature is 170 ℃, and the reaction time is 6 hours; the product is obtained by centrifugation, the centrifugation rate is 4000r/min, the time is 4min, and the yield of the target product lactic acid is 38.7% and the yield of the main by-product 5-hydroxymethylfurfural is only 11.3% by analyzing the liquid phase product by High Performance Liquid Chromatography (HPLC).
Example 10
Preparing a catalyst: mixing a commercial grade Beta molecular sieve with concentrated nitric acid (the purity is 65-68%) according to the proportion of 15g of Beta molecular sieve to 300mL of concentrated nitric acid, stirring and reacting at 90 ℃ for 24h for dealuminization, centrifuging after reaction, rinsing for many times until the supernatant is neutral, and then drying at 90 ℃ for 16h to obtain the dealuminized Beta molecular sieve; mixing 1g of dealuminized Beta molecular sieve and 337.8mg of ytterbium acetate (0.8 mmol of Yb), grinding for 30min, and then roasting at the high temperature of 550 ℃ for 6h to obtain the aluminum-free Y-Beta molecular sieve catalyst.
And (3) catalytic reaction: weighing 160mg of fructose, 115mg of aluminum-free Yb-Beta molecular sieve catalyst and 10mL of deionized water, adding the weighed materials into a polytetrafluoroethylene lining with the capacity of 50mL, placing the polytetrafluoroethylene lining into a stainless steel reaction kettle, then placing the stainless steel reaction kettle, and then placing the stainless steel reaction kettle into a rotary oven for reaction, wherein the rotating speed of the rotary oven is set to be 20r/min, the temperature is 170 ℃, and the reaction time is 6 hours; the product is obtained by centrifugation, the centrifugation rate is 4000r/min, the time is 4min, the yield of the target product lactic acid is 40.2 percent and the yield of the main byproduct 5-hydroxymethylfurfural is only 12.8 percent by analyzing the liquid phase product by adopting High Performance Liquid Chromatography (HPLC).
Comparative example 1
Preparing a catalyst: mixing a commercial grade Beta molecular sieve with concentrated nitric acid (the purity is 65-68%) according to the proportion of mixing 25g of the Beta molecular sieve with 500mL of the concentrated nitric acid, stirring and reacting for 20h at 100 ℃ for dealuminization, centrifuging after the reaction, rinsing for many times until the supernatant is neutral, and then drying for 16h at 90 ℃ to obtain the dealuminized Beta molecular sieve; mixing 1g of dealuminized Beta molecular sieve with 94.7mg of tin acetate (0.4 mmol of Sn), grinding for 30min, and then roasting at the high temperature of 550 ℃ for 6h to obtain the aluminum-free Sn-Beta molecular sieve catalyst with the best catalytic effect in the reaction of catalyzing glucose to produce lactic acid.
And (3) catalytic reaction: weighing 225mg of glucose, 160mg of aluminum-free Sn-Beta molecular sieve catalyst and 10mL of deionized water, adding into a polytetrafluoroethylene lining with the capacity of 50mL, placing in a stainless steel reaction kettle, and then putting in a rotary oven for reaction, wherein the rotating speed of the rotary oven is set to be 20r/min, the temperature is 190 ℃, and reacting for 2h; the product is obtained by centrifugation, the centrifugation rate is 4000r/min, the time is 4min, and the High Performance Liquid Chromatography (HPLC) is adopted to analyze the liquid phase product, so that the yield of the target product lactic acid is 23%, and the yield of the main byproduct 5-hydroxymethylfurfural is as high as 17.3%.
Comparative example 2
Preparing a catalyst: mixing a commercial grade Beta molecular sieve with concentrated nitric acid (the purity is 65-68%) according to the proportion of mixing 25g of the Beta molecular sieve with 500mL of the concentrated nitric acid, stirring and reacting for 20h at 100 ℃ for dealuminization, centrifuging after the reaction, rinsing for many times until the supernatant is neutral, and then drying for 16h at 90 ℃ to obtain the dealuminized Beta molecular sieve; 1g of dealuminized Beta molecular sieve and 126.4mg of lanthanum acetate (0.4 mmol of La) are mixed and ground for 30min, and then the mixture is roasted at the high temperature of 550 ℃ for 6h to obtain the non-aluminum La-Beta molecular sieve catalyst.
And (3) catalytic reaction: weighing 225mg of glucose, 160mg of aluminum-free La-Beta molecular sieve catalyst and 10mL of deionized water, adding into a polytetrafluoroethylene lining with the capacity of 50mL, placing in a stainless steel reaction kettle, and then sending to a rotary oven for reaction, wherein the rotating speed of the rotary oven is set to be 20r/min, the temperature is 190 ℃, and the reaction is carried out for 2 hours; the product is obtained by centrifugation, the centrifugation rate is 4000r/min, the time is 4min, and the yield of the target product lactic acid is 15.1 percent by analyzing the liquid phase product by adopting High Performance Liquid Chromatography (HPLC).
Comparative example 3
Preparing a catalyst: mixing a commercial grade Beta molecular sieve with concentrated nitric acid (the purity is 65% -68%) according to the proportion of mixing 25g of the Beta molecular sieve with 500mL of the concentrated nitric acid, stirring and reacting for 20h at 100 ℃ for dealuminization, centrifuging after the reaction, rinsing for many times until the supernatant is neutral, and then drying for 16h at 90 ℃ to obtain the dealuminized Beta molecular sieve; 1g of dealuminized Beta molecular sieve and 76.8mg of cesium acetate (0.4 mmol of Ce) are mixed and ground for 30min, and then the mixture is roasted at the high temperature of 550 ℃ for 6h to obtain the aluminum-free Ce-Beta molecular sieve catalyst.
And (3) catalytic reaction: weighing 225mg of glucose, 160mg of aluminum-free Ce-Beta molecular sieve catalyst and 10mL of deionized water, adding into a polytetrafluoroethylene lining with the capacity of 50mL, placing in a stainless steel reaction kettle, and then sending to a rotary oven for reaction, wherein the rotating speed of the rotary oven is set to be 20r/min, the temperature is 190 ℃, and the reaction is carried out for 2 hours; the product is obtained by centrifugation, the centrifugation speed is 4000r/min, the time is 4min, and the yield of the target product lactic acid is 7.2 percent by analyzing a liquid phase product by adopting High Performance Liquid Chromatography (HPLC).
Comparative example 4
Preparing a catalyst: mixing a commercial grade Beta molecular sieve with concentrated nitric acid (the purity is 65-68%) according to the proportion of mixing 25g of the Beta molecular sieve with 500mL of the concentrated nitric acid, stirring and reacting for 20h at 100 ℃ for dealuminization, centrifuging after the reaction, rinsing for many times until the supernatant is neutral, and then drying for 16h at 90 ℃ to obtain the dealuminized Beta molecular sieve; 1g of dealuminized Beta molecular sieve and 102.8mg of yttrium acetate (0.4 mmol Y) are mixed and ground for 30min, and then the mixture is roasted at the high temperature of 550 ℃ for 6h to obtain the aluminum-free Y-Beta molecular sieve catalyst.
And (3) catalytic reaction: weighing 225mg of glucose, 160mg of aluminum-free Y-Beta molecular sieve catalyst and 10mL of deionized water, adding into a polytetrafluoroethylene lining with the capacity of 50mL, placing in a stainless steel reaction kettle, and then placing in a rotary oven for reaction, wherein the rotating speed of the rotary oven is set to be 20r/min, the temperature is 190 ℃, and reacting for 2h; the product is obtained by centrifugation, the centrifugation rate is 4000r/min, the time is 4min, and the yield of the target product lactic acid is 27.5 percent by analyzing the liquid phase product by adopting High Performance Liquid Chromatography (HPLC).
Comparative example 5
Preparing a catalyst: mixing a commercial grade Beta molecular sieve with concentrated nitric acid (the purity is 65% -68%) according to the proportion of mixing 25g of the Beta molecular sieve with 500mL of the concentrated nitric acid, stirring and reacting for 20h at 100 ℃ for dealuminization, centrifuging after the reaction, rinsing for many times until the supernatant is neutral, and then drying for 16h at 90 ℃ to obtain the dealuminized Beta molecular sieve; mixing 1g of dealuminized Beta molecular sieve with 168.8mg of ytterbium acetate tetrahydrate (0.4 mmol of Yb), grinding for 30min, and then roasting at the high temperature of 550 ℃ for 6h to obtain the aluminum-free Yb-Beta molecular sieve catalyst.
And (3) catalytic reaction: weighing 225mg of glucose, 160mg of aluminum-free Yb-Beta molecular sieve catalyst and 10mL of deionized water, adding into a polytetrafluoroethylene inner liner with the capacity of 50mL, placing in a stainless steel reaction kettle, and then sending to a rotary oven for reaction, wherein the rotating speed of the rotary oven is set to be 20r/min, the temperature is 190 ℃, and the reaction is carried out for 2 hours; the product is obtained by centrifugation, the centrifugation rate is 4000r/min, the time is 4min, and the yield of the target product lactic acid is 25.7 percent by analyzing the liquid phase product by adopting High Performance Liquid Chromatography (HPLC).
Claims (10)
1. A preparation method of a modified Beta molecular sieve for catalytically converting biomass into lactic acid is characterized by comprising the following steps: mixing a certain amount of Beta molecular sieve with concentrated nitric acid, dealuminizing, carrying out solid-liquid separation after reaction, rinsing for multiple times, and drying to obtain the dealuminized Beta molecular sieve; uniformly mixing a certain amount of rare earth metal salt and the dealuminized Beta molecular sieve, grinding, and roasting to obtain the modified Beta molecular sieve, wherein the rare earth metal salt is yttrium salt or ytterbium salt.
2. The preparation method according to claim 1, wherein the ratio of the Beta molecular sieve to the concentrated nitric acid is 10-25g of Beta molecular sieve to 200-500mL of concentrated nitric acid; the dealumination process is carried out at the temperature of 90-120 ℃ for 18-24 h.
3. The preparation method according to claim 1, wherein the rare earth metal salt is preferably rare earth metal acetate or rare earth metal acetate hydrate, and the ratio of the rare earth metal acetate or rare earth metal acetate hydrate to the dealuminized Beta molecular sieve is 1g of dealuminized Beta molecular sieve and 0.4-1.6mmol of rare earth metal acetate/rare earth metal acetate hydrate (in terms of metal atom mol).
4. The method according to any one of claims 1 to 3, wherein the drying is performed at 90 to 130 ℃ for 8 to 16 hours.
5. The method according to any one of claims 1 to 3, wherein the drying is performed at 90 to 130 ℃ for 8 to 16 hours. The roasting condition is that roasting is carried out for 5-7h at 500-550 ℃.
6. The modified Beta molecular sieve catalyst prepared by the preparation method according to any one of claims 1 to 5.
7. A method for catalytically converting biomass to lactic acid, said method comprising: adding a quantitative reaction substrate, the modified Beta molecular sieve catalyst according to claim 6 and water into a reaction kettle for reaction, wherein the reaction substrate is added according to the following proportion: 135-250mg of reaction substrate, 100-180mg of catalyst and 10-15 mL of water.
8. The method of claim 7, wherein the reaction substrate is a carbohydrate; preferably, the saccharide is selected from glucose, sucrose and fructose.
9. The method of claim 7, wherein the reaction temperature is 160 ℃ to 230 ℃ and the reaction time is 1h to 6h.
10. The method for catalytically converting biomass into lactic acid according to any one of claims 7 to 9, wherein the catalyst is activated and reused after the reaction.
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