CN115894213A - Method for catalytically synthesizing calcium lactate and hydrogen by Cu/apatite nano-catalyst - Google Patents
Method for catalytically synthesizing calcium lactate and hydrogen by Cu/apatite nano-catalyst Download PDFInfo
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- 229910052586 apatite Inorganic materials 0.000 title claims abstract description 95
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 title claims abstract description 90
- 239000001527 calcium lactate Substances 0.000 title claims abstract description 90
- 229960002401 calcium lactate Drugs 0.000 title claims abstract description 90
- 235000011086 calcium lactate Nutrition 0.000 title claims abstract description 90
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 title claims abstract description 87
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000001257 hydrogen Substances 0.000 title claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 130
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 18
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 13
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 13
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 10
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- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims description 85
- 239000000243 solution Substances 0.000 claims description 42
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 24
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- 239000011259 mixed solution Substances 0.000 claims description 17
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- 238000001914 filtration Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 229910052587 fluorapatite Inorganic materials 0.000 claims description 7
- 229940077441 fluorapatite Drugs 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
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- 230000008025 crystallization Effects 0.000 claims description 4
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- 238000006722 reduction reaction Methods 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 claims 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 13
- 235000011187 glycerol Nutrition 0.000 abstract 6
- 238000010926 purge Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 17
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 16
- 238000006356 dehydrogenation reaction Methods 0.000 description 10
- 238000000855 fermentation Methods 0.000 description 8
- 230000004151 fermentation Effects 0.000 description 8
- 239000004310 lactic acid Substances 0.000 description 8
- 235000014655 lactic acid Nutrition 0.000 description 8
- 239000011575 calcium Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910052589 chlorapatite Inorganic materials 0.000 description 6
- PROQIPRRNZUXQM-ZXXIGWHRSA-N estriol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H]([C@H](O)C4)O)[C@@H]4[C@@H]3CCC2=C1 PROQIPRRNZUXQM-ZXXIGWHRSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
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- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
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- 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 description 1
- 241000186673 Lactobacillus delbrueckii Species 0.000 description 1
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- 150000003893 lactate salts Chemical class 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
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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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a method for synthesizing calcium lactate and hydrogen under the catalysis of a Cu/apatite nano-catalyst, which is characterized in that a glycerol aqueous solution, calcium hydroxide and the Cu/apatite nano-catalyst are added into a reaction kettle, wherein the concentration of the glycerol aqueous solution is 0.5-2mol/L; the molar ratio of the calcium hydroxide to the glycerol is 0.4-0.8:1; the mass ratio of the glycerol to the catalyst is 20:1; introducing nitrogen for purging, heating to 210-230 ℃, stirring at constant temperature for reaction for 0.5-4h to obtain calcium lactate reaction liquid and hydrogen, and concentrating and crystallizing the calcium lactate reaction liquid to obtain a calcium lactate product. The invention applies Cu/apatite nano-catalyst to catalyze glycerin to synthesize calcium lactate and hydrogen, under the optimal condition, the conversion rate of the glycerin is 100%, the selectivity of the calcium lactate is 95.2%, and the yield of the hydrogen is more than 98%. After the calcium lactate reaction liquid is concentrated and crystallized, the yield of the calcium lactate is 85.9 percent, and the purity of the calcium lactate is 96.5 percent.
Description
Technical Field
The invention belongs to the technical field of calcium lactate and hydrogen preparation, and particularly relates to a method for catalytically synthesizing calcium lactate and hydrogen by using a Cu/apatite nano catalyst.
Background
Calcium lactate and lactate salts are important chemicals in the lactic acid industry. The preparation method of calcium lactate mainly comprises neutralization reaction method and fermentation method. The neutralization reaction method mainly adopts calcium hydroxide, calcium carbonate or shell to react with lactic acid to prepare calcium lactate. The fermentation method mainly uses glucose as raw material, obtains lactic acid through microbial fermentation, and the lactic acid reacts with calcium carbonate in eggshell powder in fermentation liquor to generate calcium lactate. Zhang Ping uses wheat starch waste water double enzyme saccharification fermentation method to produce calcium lactate, adopts Lactobacillus delbrueckii, under the condition of initial sugar concentration of 7%, corn steep liquor of 3%, inoculum size of 8%, and 50 deg.C, through twice crystallization, the total yield of calcium lactate can be up to 78.9%. However, the reaction process for preparing calcium lactate by the fermentation method is relatively complicated, the impurity removal process is particularly complex, the reaction period is long, the yield is low, and the product has high impurity content.
In the prior art, the direct neutralization method for preparing the calcium lactate product has high production cost because the lactic acid is adopted as a raw material. In the prior art, the breeding cycle of the calcium lactate strain prepared by the microbial transformation method is longer, the fermentation time is long, and the yield is lower than 80%. Therefore, a new technical method which meets the actual production requirements, replaces the traditional sugar fermentation to prepare lactic acid and prepares calcium lactate by reacting lactic acid with calcium hydroxide is urgently needed in the actual production.
Glycerol is a by-product of biodiesel and is in sufficient supply on the market. Glycerol molecules containing three hydroxyl groups are useful in the synthesis of a variety of chemicals, such as 1, 2-propanediol, 1, 3-propanediol, acrolein, acrylic acid, lactic acid, and the like. The utilization rate of the downstream glycerol product in the market is not high due to the restriction of the mature degree of the technology.
The production technology of hydrogen comprises a chlor-alkali method and a coal, natural gas and residual oil steam conversion method. The chlor-alkali method in the traditional hydrogen production process has high energy consumption, and the coal, natural gas and residual oil steam conversion method not only consumes resources, but also produces carbon dioxide as a byproduct.
The preparation method for producing hydrogen by reasonably utilizing glycerol in actual production has not been reported.
Disclosure of Invention
The invention aims to solve the technical defects in the production of calcium lactate at present. The invention provides a preparation method of a Cu/apatite nano catalyst, and the Cu/apatite nano catalyst is applied to catalyzing glycerol dehydrogenation conversion and reacting with calcium hydroxide to directly synthesize calcium lactate and simultaneously produce hydrogen. The specific technical scheme is as follows:
a method for catalytically synthesizing calcium lactate and hydrogen by a Cu/apatite nano catalyst is carried out according to the following steps:
adding a glycerol aqueous solution, calcium hydroxide and a catalyst into a reaction kettle; the catalyst is a Cu/apatite nano catalyst, the concentration of the glycerol aqueous solution is 0.5-2mol/L, the addition amount of the glycerol aqueous solution is 200mL, and the molar ratio of calcium hydroxide to glycerol is 0.4:1-0.8:1, the mass ratio of the glycerol to the catalyst is 20:1; blowing nitrogen to remove air in the reaction kettle, heating to 210-230 ℃, stirring at constant temperature for reaction for 0.5-4h to obtain calcium lactate reaction liquid and hydrogen, and concentrating and crystallizing the calcium lactate reaction liquid to obtain a calcium lactate product.
Preferably, the preparation method of the Cu/apatite nano-catalyst comprises the following steps: dissolving copper nitrate trihydrate into deionized water to obtain a copper nitrate solution; adding nano apatite into deionized water, and stirring for 1h to obtain a nano apatite solution; mixing a copper nitrate solution and a nano apatite solution, heating to 60 ℃, and stirring for 1h to obtain a first mixed solution; then, dropwise adding 1.0mol/L NaOH solution into the first mixed solution to enable the pH of the first mixed solution to be 11, and stirring for 0.5h; adding a hydrazine hydrate solution with the mass fraction of 85% at the speed of 1mL/min, wherein the mole number of the hydrazine hydrate is 5 times that of the copper, stirring for reduction reaction for 4 hours to obtain a second mixed solution, and carrying out a post-treatment process on the second mixed solution to obtain the Cu/apatite nano catalyst.
Preferably, the Cu/apatite nano-catalyst consists of copper nano-particles and nano-apatite, the copper nano-particles are loaded on the nano-apatite, wherein the mass of copper element accounts for 4% -16% of the mass of the Cu/apatite nano-catalyst, and the particle size of the copper nano-particles is 1-3.5nm.
The nano apatite is a carrier of the catalyst.
When the mass percentage of the copper element in the Cu/apatite nano-catalyst is 4%, 8% or 16% based on the mass of the Cu/apatite nano-catalyst, the catalyst is abbreviated as Cu (4)/apatite, cu (8)/apatite or Cu (16)/apatite.
Preferably, the nano apatite is at least one of nano fluorapatite and nano chlorapatite, and the particle size distribution of the nano apatite is between 20 and 80 nm.
Preferably, the mass ratio of the copper nitrate trihydrate to the nano apatite is 6.04:8.4.
preferably, the mass ratio of the copper nitrate trihydrate to the nano apatite is 1.51:9.6.
preferably, the mass ratio of the copper nitrate trihydrate to the nano apatite is 3.02:9.2.
preferably, the post-treatment process is as follows: filtering the second mixed solution to obtain a solid, and washing the solid with deionized water until the conductivity of the filtrate is less than 2 mS.m -1 And then washing the mixture for three times by using absolute ethyl alcohol, and filtering the mixture to obtain the Cu/apatite nano-catalyst.
Preferably, the stirring rate is 500r/min.
Preferably, the specific steps of the concentration and crystallization are as follows: heating the calcium lactate reaction solution at 85 deg.C and stirring for 3h to dissolve all calcium lactate in the calcium lactate reaction solution, heat filtering to remove catalyst to obtain filtrate, placing the filtrate in a rotary evaporator, concentrating under reduced pressure at 80 deg.C to 50-150mL to obtain concentrated solution, placing the concentrated solution in ice water bath to crystallize calcium lactate, filtering and washing the crystallized calcium lactate, and drying at 120 deg.C for 12h to obtain calcium lactate product.
The invention adopts calcium hydroxide to provide alkaline conditions and a calcium source, and the Cu/apatite nano catalyst catalyzes glycerol dehydrogenation conversion and directly reacts with the calcium hydroxide to synthesize calcium lactate and hydrogen. In the reaction process, nano copper in the Cu/apatite nano catalyst catalyzes glycerol dehydrogenation to generate hydrogen and an intermediate (C) 3 H 6 O 3 ) Ca of intermediate adsorbed on catalyst and apatite as carrier 2+ And Ca in the reaction solution 2+ The reaction produces calcium lactate product. Ca of reaction solution in the course of reaction 2+ Can supplement Ca consumed in nanometer apatite carrier 2+ 。
The invention has the beneficial effects that:
the Cu/apatite nano-catalyst prepared by the invention is used for catalyzing glycerol dehydrogenation to synthesize calcium lactate, under the optimal condition, the glycerol conversion rate is 100%, the calcium lactate selectivity is 95.2%, and the hydrogen yield is more than 98%. After the calcium lactate reaction liquid is concentrated and crystallized, the yield of the calcium lactate is 85.9 percent, and the purity of the calcium lactate is 96.5 percent.
Drawings
FIG. 1 is a TEM image of a Cu (16)/apatite catalyst.
FIG. 2 is a histogram of the particle size distribution of Cu nanoparticles in a Cu (16)/apatite catalyst.
FIG. 3 is an HRTEM image of a Cu (16)/apatite catalyst.
Wherein: the circles in figure 1 indicate copper nanoparticles supported on a nano-apatite support. As can be seen from FIG. 1, the size of the nano-apatite support particles is between 20-80 nm; in FIG. 2, the particle size of copper nanoparticles in the Cu/apatite nano-catalyst is 1-3.5nm; in FIG. 3, the lattice diffraction fringe spacing of 0.177nm and 0.179nm corresponds to the (200) crystal face of the face-centered cubic metallic copper, the lattice diffraction fringe spacing of 0.204nm and 0.206nm corresponds to the (111) crystal face of the face-centered cubic metallic copper, and HRTEM analysis shows that the copper nanoparticles are successfully loaded on the nano apatite carrier.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to specific embodiments. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
The nano apatite is one or two of nano fluorapatite and nano chlorapatite. The nano apatite used in the present invention is in the form of nano powder.
The calcium lactate selectivity is the ratio of the actual yield of calcium lactate to the theoretical amount of conversion of glycerol to calcium lactate.
The hydrogen yield is the ratio of the actual yield of hydrogen to the theoretical amount of hydrogen generated by the conversion of glycerol.
Example 1
(1) Preparation of Cu (16)/apatite nano-catalyst
6.04g of copper nitrate trihydrate (Cu (NO) 3 ) 2 ·3H 2 O) is dissolved in 20mL of deionized water to obtain a copper nitrate solution; weighing 8.4g of carrier nano chlorapatite powder, dispersing the powder in 30mL of deionized water, and stirring for 1h to obtain a nano apatite solution; dissolving copper nitrate solution and nano apatiteThe solution was mixed and added to a 250mL round bottom flask. The mass percentage of the copper element in the Cu/apatite nano-catalyst is 16%. The temperature is kept at 60 ℃, and the mixture is stirred for 1 hour to obtain a first mixed solution. Dropwise adding 1mol/L NaOH solution into the first mixed solution, adjusting the pH value of the first mixed solution to 11, stirring for 0.5h, and dropwise adding hydrazine hydrate solution through a flow pump, wherein the mass fraction of hydrazine hydrate in the hydrazine hydrate solution is 85%, the mass of the hydrazine hydrate solution is 7.54g, and the flow rate is 1mL/min. The number of moles of hydrazine hydrate is 5 times the number of moles of copper. And after adding a hydrazine hydrate solution, continuously stirring for reduction reaction for 4 hours to obtain a second mixed solution. And filtering the second mixed solution to obtain a solid, washing the solid with deionized water for three times, washing the solid with absolute ethyl alcohol for three times, filtering to obtain the Cu/apatite nano catalyst, and storing the catalyst in the absolute ethyl alcohol.
The transmission electron microscopy examination of the Cu (16)/apatite catalyst results in FIG. 1, from which it can be seen that the particle size distribution of the nano-apatite is between 20-80 nm. According to the analysis of the results of the TEM image, FIG. 2, which is a histogram of the particle size distribution of Cu nanoparticles in the Cu (16)/apatite catalyst, is obtained, indicating that the particle size of the copper nanoparticles in the Cu/apatite catalyst is 1 to 3.5nm.
High resolution transmission electron microscope detection is carried out on the Cu (16)/apatite catalyst to obtain a figure 3, and as can be seen from the figure 3, the copper nanoparticles exist in a metal copper structure, and are successfully loaded on the nanometer apatite carrier.
(2) Catalytic reaction
A reaction vessel equipped with a thermometer, a pressure gauge and a stirrer was charged with 200mL of 2mol/L aqueous glycerol solution in terms of Ca (OH) 2 The molar ratio to glycerol was 0.6:1 adding Ca (OH) 2 1.84g of the Cu (16)/apatite nanocatalyst prepared in this example was added thereto, and N was used 2 And (3) evacuating the air in the reaction kettle, adjusting the rotating speed to 500rpm when the temperature of the reaction liquid reaches 230 ℃, and reacting for 2 hours to obtain the calcium lactate reaction liquid and hydrogen. The calcium lactate reaction solution was taken out, concentrated and crystallized to obtain calcium lactate products, which were analyzed, and the experimental results are shown in table 1.
TABLE 1 Glycerol conversion, calcium lactate selectivity, hydrogen yield from Cu (16)/apatite catalyzed dehydrogenation of glycerol to calcium lactate and hydrogen
Example 2
(1) Catalyst preparation
Example 2 preparation of catalyst the same as in example 1 preparation of Cu (16)/apatite nanocatalyst was performed, except that the amounts of copper nitrate and nanochlorapatite added in step (1) of example 1 were changed to change the mass of copper nitrate to 1.51g and 3.02g, and the mass of nanocalcite to 9.6g and 9.2g. Therefore, in example 2, the mass percentage of copper to the mass of the Cu/apatite nanocatalyst was 4% and 8%, and Cu (4)/apatite and Cu (8)/apatite nanocatalysts were prepared. The prepared catalyst is used for catalyzing glycerol dehydrogenation to prepare calcium lactate and hydrogen.
(2) Catalytic reaction
The catalytic reaction of example 2 was the same as that of step (2) of example 1, the catalyst used was the catalyst obtained in this example, and the experimental results of example 2 are shown in Table 2.
TABLE 2 Glycerol conversion, calcium lactate selectivity, hydrogen yield from the catalysis of Glycerol with Cu/Apatite of varying copper content to calcium lactate and Hydrogen
Example 3
(1) Catalyst preparation
Example 3 preparation of catalyst Cu (16)/apatite conditions the same as in step (1) of example 1, except that nano chlorapatite was replaced with nano fluoroapatite.
(2) Catalytic reaction
The procedure of the catalytic reaction was the same as that of the step (2) in example 1 except that the reaction temperatures were changed to 210 ℃ and 220 ℃ and the catalyst used was the catalyst obtained in this example, and the experimental results of example 3 are shown in Table 3.
TABLE 3 conversion rate of glycerol, selectivity of calcium lactate product, and yield of hydrogen for synthesis of calcium lactate and hydrogen by dehydrogenation conversion of glycerol with Cu (16)/apatite at different reaction temperatures
Example 4
(1) Catalyst preparation
The preparation conditions of the Cu (16)/apatite nano-catalyst are the same as the step (1) in the example 1, and only the nano-chloroapatite carrier is replaced by a nano-chloroapatite/nano-fluorapatite mixed carrier. The mass ratio of the nano chlorapatite to the nano fluorapatite in the mixed carrier of the nano chlorapatite and the nano fluorapatite is 1:1.
(2) Catalytic reaction
The other conditions and steps of the catalytic reaction were the same as in example 1, the reaction time in step (2) was changed to 0.5h, 2h and 4h, the concentration of the glycerol aqueous solution was changed to 0.5mol/L and 2mol/L, the catalyst used was the catalyst prepared in this example, and the catalytic dehydrogenation conversion of glycerol to synthesize calcium lactate and hydrogen was carried out, and the experimental results obtained are shown in Table 4.
TABLE 4 Glycerol conversion, calcium lactate selectivity, hydrogen yield for synthesis of calcium lactate and hydrogen by Cu (16)/apatite catalyzed glycerol dehydrogenation conversion with different reaction time
Example 5
(1) Catalyst preparation
The preparation conditions of the Cu (16)/apatite nano-catalyst are the same as in the step (1) of example 1.
(2) Catalytic reaction
The catalytic reaction is the same as that in the step (2) in the example 1, the molar ratio of the calcium hydroxide to the glycerol in the step (2) is changed to be 0.4. The results are shown in Table 5.
TABLE 5 Glycerol conversion, calcium lactate selectivity, hydrogen yield for synthesis of calcium lactate and hydrogen by dehydrogenation conversion of glycerol with Cu (16)/apatite at different molar ratios of calcium hydroxide to glycerol
Example 6
(1) Catalyst preparation
The preparation conditions of the Cu (16)/apatite nano-catalyst are the same as the step (1) in the example 1.
(2) Catalytic reaction
The catalytic reaction was performed in the same manner as in step (2) of example 1 to obtain a calcium lactate reaction solution and hydrogen gas.
Dissolving calcium lactate in the reaction solution at 85 deg.C. Hot filtering to remove catalyst in the reaction solution to obtain filtrate, placing the filtrate in a rotary evaporator, evaporating and concentrating under reduced pressure at 80 deg.C to 50mL, 100mL, 150mL to obtain concentrated solution, and placing the concentrated solution in ice water bath to crystallize calcium lactate. Filtering and washing the crystallized calcium lactate, and drying at 120 ℃ for 12h. The purity of the calcium lactate product was analyzed using high performance liquid chromatography. The yields of solid calcium lactate obtained were 85.9%, 82.5%, 75.2%, respectively; the purity of the obtained calcium lactate is 96.5%, 97.5% and 98.2% respectively; specific data are shown in Table 6.
TABLE 6 yield of calcium lactate solid and purity of calcium lactate by crystallization at different concentration volumes
| Volume of concentrate (mL) | Calcium lactate yield (%) | Purity of calcium lactate (%) |
| 50 | 85.9 | 96.5 |
| 100 | 82.5 | 97.5 |
| 150 | 75.2 | 98.2 |
It should be understood that the detailed description of the present invention is only for illustrating the present invention and is not limited by the technical solutions described in the embodiments of the present invention, and those skilled in the art should understand that the present invention can be modified or substituted equally to achieve the same technical effects; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (10)
1. A method for catalytically synthesizing calcium lactate and hydrogen by a Cu/apatite nano catalyst is characterized by comprising the following steps:
adding a glycerol aqueous solution, calcium hydroxide and a catalyst into a reaction kettle; the catalyst is a Cu/apatite nano catalyst, the concentration of the glycerol aqueous solution is 0.5-2mol/L, the addition amount of the glycerol aqueous solution is 200mL, and the molar ratio of calcium hydroxide to glycerol is 0.4:1-0.8:1, the mass ratio of the glycerol to the catalyst is 20:1; blowing nitrogen to remove air in the reaction kettle, heating to 210-230 ℃, stirring at constant temperature for reaction for 0.5-4h to obtain calcium lactate reaction liquid and hydrogen, and concentrating and crystallizing the calcium lactate reaction liquid to obtain a calcium lactate product.
2. The method for catalytic synthesis of calcium lactate and hydrogen gas by using the Cu/apatite nano-catalyst according to claim 1, wherein the Cu/apatite nano-catalyst is prepared by the following steps: dissolving copper nitrate trihydrate into deionized water to obtain a copper nitrate solution; adding nano apatite into deionized water, and stirring for 1h to obtain a nano apatite solution; mixing a copper nitrate solution and a nano apatite solution, heating to 60 ℃, and stirring for 1h to obtain a first mixed solution; then, dropwise adding 1.0mol/L NaOH solution into the first mixed solution to enable the pH of the first mixed solution to be 11, and stirring for 0.5h; adding a hydrazine hydrate solution with the mass fraction of 85% at the speed of 1mL/min, wherein the mole number of the hydrazine hydrate is 5 times that of the copper, stirring for reduction reaction for 4 hours to obtain a second mixed solution, and carrying out a post-treatment process on the second mixed solution to obtain the Cu/apatite nano catalyst.
3. The method for catalytically synthesizing calcium lactate and hydrogen gas by using the Cu/apatite nano-catalyst according to claim 1, wherein the Cu/apatite nano-catalyst is composed of copper nanoparticles and nano-apatite, the copper nanoparticles are loaded on the nano-apatite, the mass of the copper element accounts for 4% -16% of the mass of the Cu/apatite nano-catalyst, and the particle size of the copper nanoparticles is 1-3.5nm.
4. The method for catalytic synthesis of calcium lactate and hydrogen with the Cu/apatite nano-catalyst according to claim 2, wherein the nano-apatite is at least one of nano-fluorapatite and nano-chloroapatite, and the particle size distribution of the nano-apatite is between 20 nm and 80 nm.
5. The method for catalytic synthesis of calcium lactate and hydrogen by using the Cu/apatite nano-catalyst according to claim 2, wherein the mass ratio of the copper nitrate trihydrate to the nano-apatite is 6.04:8.4.
6. the method for catalytically synthesizing calcium lactate and hydrogen gas by using the Cu/apatite nano-catalyst according to claim 2, wherein the mass ratio of the copper nitrate trihydrate to the nano-apatite is 1.51:9.6.
7. the method for catalytically synthesizing calcium lactate and hydrogen gas by using the Cu/apatite nano-catalyst according to claim 2, wherein the mass ratio of the copper nitrate trihydrate to the nano-apatite is 3.02:9.2.
8. the method for catalytic synthesis of calcium lactate and hydrogen gas by using Cu/apatite nano-catalyst according to claim 2, wherein the post-treatment process comprises: filtering the second mixed solution to obtain a solid, and washing the solid with deionized water until the conductivity of the filtrate is less than 2 mS.m -1 Then washing the solution for three times by using absolute ethyl alcohol, and filtering the solution to obtain the Cu/apatite nano catalyst.
9. The method for catalytic synthesis of calcium lactate and hydrogen gas with Cu/apatite nanocatalyst according to claim 1, characterized in that the stirring rate is 500r/min.
10. The method for catalytic synthesis of calcium lactate and hydrogen by using Cu/apatite nano-catalyst according to claim 1, characterized in that the concentration and crystallization comprises the following steps: heating the calcium lactate reaction solution at 85 deg.C and stirring for 3h to dissolve all calcium lactate in the calcium lactate reaction solution, heat filtering to remove catalyst to obtain filtrate, placing the filtrate in a rotary evaporator, concentrating under reduced pressure at 80 deg.C to 50-150mL to obtain concentrated solution, placing the concentrated solution in ice water bath to crystallize calcium lactate, filtering and washing the crystallized calcium lactate, and drying at 120 deg.C for 12h to obtain calcium lactate product.
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