CN113956149B - Separation method of glyceric acid product prepared by glycerol oxidation - Google Patents
Separation method of glyceric acid product prepared by glycerol oxidation Download PDFInfo
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 216
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 title claims abstract description 56
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 title claims abstract description 56
- 238000000926 separation method Methods 0.000 title claims abstract description 37
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 31
- 230000003647 oxidation Effects 0.000 title claims abstract description 27
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 claims abstract description 94
- 235000011187 glycerol Nutrition 0.000 claims abstract description 75
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000000203 mixture Substances 0.000 claims abstract description 61
- 229940120503 dihydroxyacetone Drugs 0.000 claims abstract description 49
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 28
- 238000005192 partition Methods 0.000 claims description 26
- 238000010992 reflux Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229910002848 Pt–Ru Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 10
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 30
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
-
- 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
- Y02P20/10—Process efficiency
Abstract
A process for separating the products from glyceric acid by oxidizing glycerin features that a double-tower continuous rectification is used to divide the tower with vertical wall into four segments for separating the mixture F of glycolic acid, glyceraldehyde, dihydroxyacetone, glycerin and glyceric acid. The mixture F enters from the middle part of a first prefractionation section of the tower to finish the separation of glycerin and glyceric acid; and (3) separating the light components from the glycerol in the main tower section, laterally extracting the glycerol from the middle part of the main tower section of the tower, extracting the light components from the top of the public rectifying section, and extracting the heavy component glyceric acid from the bottom of the public stripping section. The light component enters the middle part of a second prefractionation section of the tower, and glycolic acid, glyceraldehyde and dihydroxyacetone are obtained from the top of the tower, the middle part of the main tower section and the bottom of the tower respectively, so that the separation of selective oxidation products of the glycerol is realized. Under the same separation requirement, compared with the conventional four-tower vacuum rectification, the method can reduce equipment investment and heat load of a tower top condenser and a tower bottom reboiler, and solves the problem of high energy consumption in the rectification process.
Description
Technical Field
The invention belongs to the technical field of biomass chemical industry, and particularly relates to a preparation method of glyceric acid, in particular to a method for separating and purifying glyceric acid under reduced pressure.
Background
In recent years, due to the increasing exhaustion of fossil resources, research and popularization of renewable alternative energy sources are increasingly important. Biodiesel is considered as a renewable energy source with development prospect due to the advantages of good safety performance, environmental friendliness, renewable raw material sources, and the like. However, since a large amount of glycerin (the side yield is 10 wt%) is produced in the production process of biodiesel, the glycerin yield is far greater than that, and a great impact is caused to the conventional glycerin production enterprises. Therefore, the research of the conversion of glycerol into high value-added products has important practical significance. At present, the selective oxidation of glycerol is one of the important ways of the conversion and utilization of the glycerol, and a plurality of different carboxylic acid products (such as glyceric acid, dihydroxyacetone, glyceraldehyde and the like) can be obtained, and have great potential value in the industries of foods, medicines and the like. Therefore, in recent years, research on the selective oxidation of glycerol to produce carboxylic acids with high added value has been increasing.
However, the prior studies have little relevance to how to isolate glycerol oxidation products. The reason is mainly that the compounds such as glycerol, glycollic acid, glyceraldehyde, dihydroxyacetone and the like are heat-sensitive high-boiling-point compounds, are easy to decompose or polymerize when heated, and cannot be separated by adopting a conventional rectification means. And other separation methods such as ion exchange resin, membrane separation and the like are adopted, so that a glyceric acid product with high purity cannot be obtained. Therefore, based on the molecular distillation theory, the method of vacuum rectification is adopted to control the temperature of the tower bottom to be lower than the decomposition or polymerization temperature of the glycerin oxidation product, which is clearly a better way for separating the glycerin oxidation product.
For the separation of five-component glycolic acid, glyceraldehyde, dihydroxyacetone, glycerol and glyceric acid, at least four towers are needed to achieve the required separation effect by adopting a conventional vacuum rectifying tower, but the method has the defects of large investment, large energy consumption and high operation cost.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to improve the separation efficiency of glyceric acid which is a glycerol oxidation product, reduce energy consumption and the like.
The invention relates to a separation method for preparing glyceric acid products by oxidizing glycerol, which comprises the steps of obtaining a mixture F after the glyceric acid products are dehydrated, obtaining three fractions after the mixture is rectified and separated by a first partition tower, wherein the first fraction mainly comprises a mixture of glycolic acid, glyceraldehyde and dihydroxyacetone, the second fraction mainly comprises glycerol, and the third fraction mainly comprises glyceraldehyde;
and rectifying and separating the first fraction by a second partition tower to obtain a fourth fraction, a fifth fraction and a sixth fraction, wherein the fourth fraction mainly comprises glycolic acid, the fifth fraction mainly comprises glyceraldehyde, and the sixth fraction mainly comprises dihydroxyacetone.
The preparation method of glyceric acid comprises the following steps: the glycerol and the oxidant are subjected to oxidation reaction under the action of a catalyst, the reaction temperature is 20-100 ℃, and the reaction pressure is 0.1-1.5 MPa, so that the product containing glyceric acid is obtained.
In the application, the glyceric acid mixture obtained by catalytic oxidation of glycerol can be separated from four substances of glycolic acid, glycerol, glyceric acid, glyceraldehyde and dihydroxyacetone by adopting a method of rectifying in a partition tower through two partition towers, so that the separation efficiency is high, and the energy consumption is reduced. By controlling the rectification conditions, the purity of the five separated products is good.
Drawings
FIG. 1 is a process flow diagram of an energy efficient method for separating glycerol-selective oxidation products using a divided wall column under reduced pressure.
Fig. 2 is a flow chart of a conventional four-column continuous vacuum rectification process.
In fig. 1: 1-a first prefractionation section of the column; 2-a main tower section of the tower; 3-column-common rectifying section; 4-tower-public stripping section; 5-a second prefractionation section; 6-tower two main tower sections; 7-a second common rectifying section of the tower; 8-a second common stripping section; f-glycolic acid, glyceraldehyde, dihydroxyacetone, glycerol, and glyceric acid mixtures; d (D) 1 -glycolic acid, glyceraldehyde and dihydroxyacetone mixtures; s is S 1 -glycerol; w (W) 1 -glyceric acid; d (D) 2 -glycolic acid; s is S 2 -glyceraldehyde; w (W) 2 Dihydroxyacetone.
In fig. 2: f' -glycolic acid, glyceraldehyde, dihydroxyacetone, glycerol, and glyceric acid mixtures; d (D) 1 Mixtures of' -glycolic acid, glyceraldehyde and dihydroxyacetone; w (W) 1 Mixtures of' -glyceric acid with glycerol; d (D) 2 ' glycerin; w (W) 2 ' -glyceric acid; d (D) 3 ' -glycolic acid; w (W) 3 Mixtures of' -dihydroxyacetone with glyceraldehyde; d (D) 4 ' -glyceraldehyde; w (W) 4 ' -dihydroxyacetone.
Detailed Description
The separation process of the products of the glycerol oxidation to glyceric acid of the present application is described in further detail below. And do not limit the scope of the application, which is defined by the claims. Certain disclosed specific details provide a thorough understanding of the various disclosed embodiments. However, one skilled in the relevant art will recognize that embodiments can be practiced without one or more of the specific details, with other materials, etc.
In the description and in the claims, the terms "comprising," including, "and" containing "are to be construed as open-ended, meaning" including, but not limited to, unless the context requires otherwise.
Reference in the specification to "an embodiment," "one embodiment," "another embodiment," or "certain embodiments," etc., means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, it is not necessary for an "embodiment," "one embodiment," "another embodiment," or "certain embodiments" to refer to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. The various features disclosed in the specification may be replaced by alternative features serving the same, equivalent or similar purpose. Thus, unless expressly stated otherwise, the disclosed features are merely general examples of equivalent or similar features.
The term "atmospheric pressure" refers to one atmosphere of pressure, the pressure of gas produced by the atmosphere in which humans live. Each place is generally considered to be a standard atmospheric pressure, namely 100KPa or 0.1MPa, due to geographical location, altitude, temperature, etc.
The term "reflux ratio" refers to the ratio of the reflux flow L from the top of the rectifying column back into the column to the top product flow D, i.e. r=l/D. The magnitude of the reflux ratio.
The "dividing wall column" herein means that a dividing wall is provided in the column along the axial direction to divide the middle portion of the column into two parts. The feed is first pre-fractionated in one side of the middle part of the column, the light fraction rises to the upper part of the column, the light fraction and the heavy fraction are separated in the upper part of the column, the recombinant fraction flows to the lower part of the column, and the liquid phase at the top of the column and the gas phase at the bottom of the column flow to the other side of the partition wall respectively. The final middle distillates are collected in the middle part of the tower and are extracted from the other side of the partition board.
The term "overhead temperature" refers to the overhead condenser temperature and "bottom temperature" refers to the bottom reboiler temperature.
A separation method for preparing glyceric acid product by glycerol oxidation comprises the steps of removing water from the glyceric acid product to obtain a mixture F, rectifying and separating the mixture by a first partition tower to obtain three fractions, wherein the first fraction mainly comprises mixture of glycolic acid, glyceraldehyde and dihydroxyacetone, the second fraction mainly comprises glycerol, and the third fraction mainly comprises glyceraldehyde;
and rectifying and separating the first fraction by a second partition tower to obtain a fourth fraction, a fifth fraction and a sixth fraction, wherein the fourth fraction mainly comprises glycolic acid, the fifth fraction mainly comprises glyceraldehyde, and the sixth fraction mainly comprises dihydroxyacetone.
In the present application, the glyceric acid product is first subjected to water removal and formic acid removal to give mixture F. And (3) performing normal pressure rectification under the conditions of separating at the temperature of 95-105 ℃ and normal pressure, and separating formic acid, water and the like from the mixture A. Mixture F mainly comprises glycolic acid, glyceraldehyde, dihydroxyacetone, glycerol and glyceric acid mixtures.
The rectification ratio of the atmospheric tower can be between 3 and 8, and the reflux ratio is preferably 5.
In the methods for producing glyceric acid disclosed or used in the prior art, the glyceric acid is usually separated from the reaction product by an ion exchange resin or the like. However, the inventors have found that the purity of the isolated glyceric acid is to be further improved, irrespective of the isolation method used in the prior art.
The first dividing wall tower and the second dividing wall tower comprise four tower sections, and specifically, the first dividing wall tower comprises a first pre-distillation section, a first main tower section, a first public distillation section and a first public stripping section; the second divided wall column includes a second pre-distillation section, a second main column section, a second common rectification section, and a second common stripping section.
In certain embodiments, mixture F enters the first pre-distillation section of the first divided wall column where the separation of light, heavy and intermediate components is performed, the light components glycolic acid, glyceraldehyde and dihydroxyacetone are separated from the top of the first common rectification section, the intermediate component glycerol is separated from the first main column section, and the heavy component glyceric acid is separated from the first common stripping section.
In certain embodiments, the first prefractionation section and the first main column section of the first divided wall column each have 10 to 20 theoretical plates, preferably the number of theoretical plates in the first prefractionation section and the first main column section of the first divided wall column is 15; the first public rectifying section and the first public stripping section are respectively provided with 8-12 theoretical plates, and the number of the theoretical plates of the first public rectifying section and the first public stripping section is preferably 10.
By setting the theoretical plate number, heavy components, light components and intermediate components can be effectively separated.
The operation temperature in the first dividing wall column is controlled to be 80-205 ℃; the operating pressure is 6 to 10kPa.
In certain embodiments, the first divided wall column has a molar reflux ratio of from 4 to 40; preferably the reflux ratio is 8.
In certain embodiments, mixture F (including the glycolic acid, glyceraldehyde, dihydroxyacetone, glycerol, and glyceric acid mixture) is fed at a temperature of 20 to 100 ℃; the preferred feed temperature is 40℃to 60 ℃. .
Further, in certain embodiments, the light components glycolic acid, glyceraldehyde and dihydroxyacetone separated by the first divided wall column enter the second prefractionation section of the second divided wall column, are separated in the second main column section of the second divided wall column, glycolic acid is separated by the top of the second common rectification section, glyceraldehyde is separated from the second main column section, and dihydroxyacetone is separated from the common stripping section.
In certain embodiments, the second prefractionation section and the second main column section of the second divided wall column each have 30 to 50 theoretical plates, preferably 40 theoretical plates; the second public rectifying section and the second public stripping section are respectively provided with 8-12 theoretical plates, and the number of the theoretical plates is preferably 10.
By setting the theoretical plate number, heavy components, light components and intermediate components can be effectively separated.
The operation temperature in the second dividing wall column is controlled to be 80-205 ℃; the operating pressure is 6 to 10kPa.
In certain embodiments, the second divided wall column has a molar reflux ratio of from 4 to 40; preferably the reflux ratio is 35.
The materials separated by the method are separated from each other, and the mass fraction (purity) of each separated material can reach 99%.
In addition, by adopting the separation process of the bulkhead tower, compared with the conventional vacuum rectification under the same separation requirement, the separation energy consumption (the sum of heat loads of tower top condensers and tower kettle reboilers of all tower equipment) can be reduced. Solves the problem of high energy consumption in the separation process of the selective oxidation products of the glycerol. And the purity of the separated substances is high.
The preparation process of glyceric acid can adopt catalyst and technological parameters to make catalytic oxidation reaction.
Preferably, the catalyst of the glycerin catalytic oxidation reaction is one, two or more than two mixed catalysts of a single-metal platinum catalyst or a double-metal platinum-based catalyst, and the temperature is controlled to be 20-100 ℃. By carrying out the reaction under such conditions, the production of substances other than glyceric acid, dihydroxyacetone and glyceraldehyde can be well controlled or reduced. Particularly, the temperature is controlled at 70-90 ℃ and the pH is controlled at 4-5, the types and the contents of byproducts of substances except glyceric acid, dihydroxyacetone and glyceraldehyde are greatly reduced, and the byproducts are relatively easy to rectify under normal pressure.
In some embodiments, the oxidizing agent in the present application may be oxygen or hydrogen peroxide, or other substances that can oxidize glycerol. Oxygen is preferred in this application.
In some embodiments, the reaction pressure of the glycerol oxidation process is controlled between 0.1 and 1.5Mpa, with a reaction pressure of 1.0Mpa being preferred.
In some embodiments, the reaction pressure of the glycerol oxidation process is controlled to a reaction time of 4 to 16 hours, preferably 12 hours.
In some embodiments, the amount of oxygen to glycerol material (1.1-2) is 1, preferably the ratio of oxygen to glycerol material is 1.2:1.
in some embodiments, the catalyst for glycerol oxidation is selected from one, two or a mixture of more than two of a single metal platinum catalyst or a bimetallic platinum-based catalyst.
In certain embodiments, the glycerol oxidation catalyst is a bimetallic platinum-based catalyst, including one or more of Pt-Fe, pt-Ni, pt-Co, pt-Ru, pt-Cu, pt-Zn, pt-Mn, pt-Ca, and the like. Preferably, a Pt-Ru bimetallic platinum-based catalyst or a Pt-Mn bimetallic platinum-based catalyst.
Under the catalysis of excessive oxygen and glycerin under the Pt-Ru bimetallic platinum-based catalyst, the yield and selectivity of glyceric acid are high under the condition that the temperature is 20-100 ℃ (preferably 70-90 ℃), and the pressure is 0.1-1.5 Mpa (preferably 1.0 Mpa). At too high or too low a reaction temperature, the yield and selectivity of glyceric acid decrease. In the case where glycerol oxidation is carried out under such conditions, oxidation product byproducts such as formic acid and glycolic acid are more easily separated from the liquid phase separation product a. The method is favorable for separating each component in the liquid phase product A in the subsequent rectification separation, and high purification purity is maintained.
In certain embodiments, the mass ratio of glycerol reactant to the mass of Pt element in the bimetallic platinum-based catalyst is (400-600): 1. Preferably, the mass ratio of the glycerol reactant to the Pt element in the bimetallic platinum-based catalyst is 520:1
In some embodiments, the bimetallic Pt-Ru catalyst has a bimetallic Pt to Ru mass ratio of about (0.8 to 1.1): 1. Under the action of the catalyst, the yield and selectivity of the target product glyceric acid are both optimal values.
In another embodiment, the bimetallic Pt-Mn catalyst has a bimetallic Pt to Mn mass ratio of about (1.4 to 1.6): 1. The yield and selectivity of glyceric acid are both improved.
Carriers for bimetallic platinum-based catalysts include, but are not limited to, activated carbon, zeolite molecular sieves, or Al 2 O 3 Etc.
The bimetallic catalysts of the present application may be prepared by any of the methods of the prior art, such as impregnation, co-precipitation, or sol-gel methods.
By adopting the separation and purification process of the glycerol oxidation product by adopting the partition tower for reduced pressure rectification, only double towers are needed to realize the required separation task, and the equipment investment and the operation cost are greatly reduced. Solves the problem that the raw materials, main and byproducts are heated and decomposed in the production of glyceric acid, and the mass fraction of the glyceric acid, glyceraldehyde and dihydroxyacetone obtained by separation can reach 99 percent.
Example 1
Using the scheme shown in FIG. 1, the mixture F to be separated (comprising glycolic acid, glyceraldehyde, dihydroxyacetone, glycerol and glyceric acid) is fed through the middle of the first prefractionation section 1 of the first divided wall column, and the mixture D of light components glycolic acid, glyceraldehyde and dihydroxyacetone is completed in the first main column section 2 of the first divided wall column 1 With intermediate component glycerol S 1 Is separated from the other components. Glycerol S 1 A mixture D of glycolic acid, glyceraldehyde and dihydroxyacetone is separated from the middle side line of the first main tower section 1 Separating the heavy component glyceric acid W from the top of the first common rectifying section 3 1 Separated from the bottom of the first common lifting section 4. Wherein, the feeding amount of the mixture F is 40kmol/h, the mol ratio is 4:8:8:15:65, and the feeding temperature is 40 ℃; 15 theoretical plates are respectively arranged in a first prefractionation section and a first main tower section of the adopted first partition tower, 10 theoretical plates are respectively arranged in a first public rectification section and a first public stripping section, the reflux ratio is 8, the operating pressure is 7kPa, the operating temperature of the first partition tower is 90-95 ℃ at the top of the tower, and the temperature of the bottom of the tower is 198-203 ℃.
Light component mixture D 1 Feeding into the middle part of a second pre-splitting section 5 of a second dividing wall tower, completing further rectification separation in a second main tower section 6, and obtaining glycollic acid D 2 Separated from the top of the second common rectification section 7, glyceraldehyde S 2 Dihydroxyacetone is separated from the middle side line of the second main tower section 6 and dihydroxyacetone is separated from the bottom of the second common stripping section 8. Wherein, the second prefractionation section and the second main tower section of the second partition tower are respectively provided with 40 theoretical plates, the second public rectification section and the second public stripping section are respectively provided with 10 theoretical plates, the reflux ratio is 35, the operating pressure is 8kPa, the operating temperature of the second partition tower is the tower top of 90-95 ℃, and the towerThe bottom temperature is 135-145 ℃.
The final energy consumption results are shown in Table 1. The mass purities of the separated glyceric acid, glyceraldehyde and dihydroxyacetone are 99.4%,99.3% and 99.2%, respectively.
By separating the same amount of mixture F as compared to the conventional vacuum distillation of comparative example 1, the method of vacuum distillation of the present application reduces energy consumption and shortens the process line of separation.
Example two
Using the scheme shown in FIG. 1, the mixture F to be separated (comprising glycolic acid, glyceraldehyde, dihydroxyacetone, glycerol and glyceric acid) is fed through the middle of the first prefractionation section 1 of the first divided wall column, and the mixture D of light components glycolic acid, glyceraldehyde and dihydroxyacetone is completed in the first main column section 2 of the first divided wall column 1 With intermediate component glycerol S 1 Is separated from the other components. Glycerol S 1 A mixture D of glycolic acid, glyceraldehyde and dihydroxyacetone is separated from the middle side line of the first main tower section 1 Separating the heavy component glyceric acid W from the top of the first common rectifying section 3 1 Separated from the bottom of the first common lifting section 4. Wherein, the feeding amount of the mixture F is 80kmol/h, the mol ratio is 4:8:8:15:65, and the feeding temperature is 60 ℃; the first prefractionation section and the first main tower section of the first partition tower are respectively provided with 35 theoretical plates, the first public rectification section and the first public stripping section are respectively provided with 9 theoretical plates, the reflux ratio is 9, the operating pressure is 7kPa, the operating temperature of the first partition tower is 90-95 ℃ at the top of the tower, and the bottom of the tower is 198-203 ℃.
Light component mixture D 1 Feeding into the middle part of a second pre-splitting section 5 of a second dividing wall tower, completing further rectification separation in a second main tower section 6, and obtaining glycollic acid D 2 Separated from the top of the second common rectification section 7, glyceraldehyde S 2 Dihydroxyacetone is separated from the middle side line of the second main tower section 6 and dihydroxyacetone is separated from the bottom of the second common stripping section 8. Wherein the second prefractionation section and the second main column section of the second divided wall column are respectively provided with 38 theoretical plates, the second common rectification section and the second common stripping section are respectively provided with 9 theoretical plates, the reflux ratio is 37, the operating pressure is 6kPa, and the operating temperature of the second divided wall column is 9 at the top of the columnThe temperature is 0-95 ℃, and the bottom of the tower is 135-145 ℃.
The final energy consumption results are shown in Table 1. The purity of the glyceric acid, glyceraldehyde and dihydroxyacetone which are separated out is 99.3%,99.1% and 99.1%.
By separating the same amount of mixture F as compared to the conventional reduced pressure distillation of comparative example 2, the reduced pressure distillation process of the present application reduces energy consumption and shortens the separation process line.
Comparative example one
Using the procedure shown in FIG. 2, the composition, flow and temperature of the feed were maintained constant, as described in example 1. Unlike example 1, a conventional vacuum rectification apparatus was employed, i.e., four rectification columns were required. The mixture F enters a tower from the middle part of the tower to be rectified and separated, and the light component D is separated from the top of the tower 1 ' (comprising mixture of glycolic acid, glyceraldehyde and dihydroxyacetone), and separating heavy component W from tower bottom 1 ' (including glyceric acid and glycerol mixtures).
D 1 The mixture enters a tower from the three middle parts of the tower to be rectified and separated, and light component D is separated from the top of the tower 3 ' glycolic acid, heavy component W is separated from the bottom of the tower 3 ' (including dihydroxyacetone and glyceraldehyde mixtures).
W 3 The mixture enters the tower from the four middle parts of the tower to be rectified and separated, and the light component D is separated from the top of the tower 4 ' glyceraldehyde, and the heavy component W is separated from the bottom of the tower 4 ' dihydroxyacetone.
W 1 The mixture enters a tower from the middle part of the second tower to be rectified and separated, and D is separated from the top of the tower 2 ' Glycerol, W is separated from the bottom of the column 2 ' glyceric acid.
Wherein the tower has 15 theoretical plates in total, feeding is carried out at the 7 th plate, the reflux ratio is 4, the feeding temperature is 55 ℃, and the operation pressure is 7kPa; the second tower has 18 theoretical plates, the 8 th plate is fed, the reflux ratio is 4, the operating temperature is 90 ℃, and the operating pressure is 7kPa; the third tower has 12 theoretical plates, the 6 th plate is fed, the reflux ratio is 4, the operating temperature is 85 ℃, and the operating pressure is 6kPa; the four towers are provided with 55 theoretical plates, the 22 th plate is fed, the reflux ratio is 40, the operating temperature is 100 ℃, and the operating pressure is 6kPa; the results are shown in Table 1.
Table 1 example-comparison of results of separation of glycerol oxidation products by vacuum distillation with a divided wall column and conventional distillation
Comparative example two
Using the procedure shown in FIG. 2, the composition, flow and temperature of the feed were maintained constant, as described in example 2. Unlike example 2, a conventional vacuum rectification apparatus was employed, i.e., four rectification columns were required. The mixture F enters a tower from the middle part of the tower to be rectified and separated, and the light component D is separated from the top of the tower 1 ' (comprising mixture of glycolic acid, glyceraldehyde and dihydroxyacetone), and separating heavy component W from tower bottom 1 ' (including glyceric acid and glycerol mixtures).
D 1 The mixture enters a tower from the three middle parts of the tower to be rectified and separated, and light component D is separated from the top of the tower 3 ' glycolic acid, heavy component W is separated from the bottom of the tower 3 ' (including dihydroxyacetone and glyceraldehyde mixtures).
W 3 The mixture enters the tower from the four middle parts of the tower to be rectified and separated, and the light component D is separated from the top of the tower 4 ' glyceraldehyde, and the heavy component W is separated from the bottom of the tower 4 ' dihydroxyacetone.
W 1 The mixture enters a tower from the middle part of the second tower to be rectified and separated, and D is separated from the top of the tower 2 ' Glycerol, W is separated from the bottom of the column 2 ' glyceric acid.
Wherein the tower has 15 theoretical plates in total, the 7 th plate is fed, the reflux ratio is 4, the feeding temperature is 65 ℃, and the operating pressure is 7kPa; the second tower has 18 theoretical plates, the 8 th plate is fed, the reflux ratio is 4, the feeding temperature is 95 ℃, and the operating pressure is 7kPa; the third tower has 12 theoretical plates, the 6 th plate is fed, the reflux ratio is 4, the feeding temperature is 90 ℃, and the operating pressure is 6kPa; the four towers are provided with 55 theoretical plates, the 22 th plate is fed, the reflux ratio is 40, the feeding temperature is 105 ℃, and the operating pressure is 6kPa; the results are shown in Table 1.
Table 2 example two comparison of results of separation of glycerol oxidation products by vacuum distillation in a divided wall column with conventional distillation
Example III
10kmol of glycerin is injected from the bottom of the kettle type reactor 1, 14kmol of oxygen enters the reactor from the top, and the raw material reacts for 14 hours under the condition of 40 ℃ and 0.8Mpa under the action of a bimetallic Pt-Ru catalyst and then leaves the reactor.
The products of the glycerol oxidation reaction enter a gas-liquid separator for gas-liquid separation, and the oxygen of the reaction gas phase products is circulated to the top of the kettle type reactor and is mixed with the raw material oxygen; and (3) feeding the reaction liquid phase product into an atmospheric rectification tower, rectifying under atmospheric pressure at the bottom temperature of about 95-105 ℃ under the condition of separating under the atmospheric pressure, and separating formic acid, water and the like from the mixture A. Mixture F mainly comprises glycolic acid, glyceraldehyde, dihydroxyacetone, glycerol and glyceric acid mixtures.
And (3) carrying out vacuum rectification on the mixture F by using a bulkhead column according to the method of the first and second embodiments, and separating oleic acid, glyceraldehyde and dihydroxyacetone.
Example IV
The preparation process of the catalyst for synthesizing Pt-Ru by loading metal by an isovolumetric impregnation method (the mass ratio of Pt to Ru is 1:1) comprises the following steps:
(1) 1.25mL of H was taken 2 PtCl 6 ·6H 2 O solution (concentration 0.039 mol/L) and 2.16mL RuCl 3 ·6H 2 O (0.040 mol/L) and diluted in 8mL deionized water (1 g MCM-41 support water absorption capacity about 8 mL);
(2) Immersing the material in a 25mL beaker containing 1g of MCM-41 carrier, standing for more than 6h, and drying the obtained material for 3h at 100 ℃;
(3) Then roasting for 2 hours at 450 ℃ (heating rate 5 ℃/min);
(4) The roasted catalyst is treated in H 2 Reducing for 5h at 350 ℃ in Ar (1:9) mixed gas to obtain the Pt-Ru catalyst.
Example five
The carrier mesoporous MCM-41 molecular sieve of the catalyst for implementing the fourth step can be a commercially available product or can be self-prepared. The carrier is synthesized by adopting a hydrothermal method, and the specific preparation method is as follows:
(1) 2.7g of cetyltrimethylammonium bromide (CTAB) was dissolved in 125mL of deionized water, followed by addition of 33mL of ammonia to allow complete dissolution of the templating agent;
(2) 14mL of tetraethyl orthosilicate was slowly added dropwise to the above solution, the temperature was kept at 35℃and stirred for 0.5
(3) Transferring the formed emulsion solution into a crystallization kettle for crystallization for 52 hours at 110 ℃, opening the kettle for suction filtration after crystallization, washing with deionized water until the pH is approximately equal to 7, and drying for 12 hours at 100 ℃ to obtain a white powdery sample;
(4) And (3) placing the unfired sample into a muffle furnace to be roasted for 6 hours at 550 ℃ (the heating rate is 5 ℃/min) to obtain the MCM-41 molecular sieve.
The present application is described in detail for the purpose of enabling those skilled in the art to understand the contents of the present application and to implement the same, and is not limited in scope by the present application, and all equivalent changes or modifications made according to the spirit of the present application should be covered in the scope of the present application.
Claims (7)
1. A separation method for preparing glyceric acid products by glycerol oxidation comprises the steps of obtaining a mixture F after the glyceric acid products are dehydrated, enabling the mixture F to enter a first pre-distillation section of a first partition tower, separating light components, heavy components and intermediate components in a first main tower section of the first partition tower, separating light components glycolic acid, glyceraldehyde and dihydroxyacetone from the top of a first public distillation section, separating intermediate components glycerol from the first main tower section, and separating heavy components glyceric acid from the first public distillation section; the feeding temperature of the mixture F is 20-100 ℃, and the mixture F comprises glycolic acid, glyceraldehyde, dihydroxyacetone, glycerol and glyceric acid mixture; the operation temperature of the first partition tower is 90-95 ℃ at the top of the tower, 198-203 ℃ at the bottom of the tower, 7kPa, and the reflux ratio of the first partition tower is 8; the light components of glycolic acid, glyceraldehyde and dihydroxyacetone separated by the first partition tower enter a second prefractionation section of a second partition tower, are separated in a second main tower section of the second partition tower, the glycolic acid is separated out by the top of a second public rectifying section, the glyceraldehyde is separated out of the second main tower section, and the dihydroxyacetone is separated out of the public stripping section; the operation temperature of the second partition tower is 90-95 ℃ at the top of the tower, 135-145 ℃ at the bottom of the tower, the operation pressure is 8kPa, and the reflux ratio of the second partition tower is 35;
wherein, the first prefractionation section and the first main tower section of the first partition tower are respectively provided with 15 theoretical plates, and the first public rectification section and the first public stripping section are respectively provided with 10 theoretical plates; the second prefractionation section and the second main tower section of the second partition tower are respectively provided with 40 theoretical plates, and the second public rectification section and the second public stripping section are respectively provided with 10 theoretical plates;
the preparation method of the glyceric acid product comprises the following steps: in the presence of a Pt-Ru bimetallic platinum-based catalyst, the reaction pressure is controlled to be 0.1-1.5 MPa, the reaction temperature is controlled to be 20-100 ℃, and glycerol is oxidized into a glyceric acid product.
2. The separation process according to claim 1, wherein the feed temperature of the mixture F is 40 ℃ to 60 ℃.
3. The separation method according to any one of claims 1 to 2, wherein the reaction pressure of the glycerol oxidation process is controlled to be 1.0MPa;
the reaction pressure in the glycerol oxidation process is controlled to be 1.0MPa, and the reaction time is controlled to be 4-16 h.
4. The separation method according to any one of claims 1 to 2, wherein the reaction time for controlling the reaction pressure of the glycerol oxidation process to 1.0MPa is 12 hours.
5. The separation method according to any one of claims 1 to 2, characterized in that the mass ratio of glycerin to the substance of Pt element in the bimetallic platinum-based catalyst is (400 to 600): 1.
6. The separation method according to any one of claims 1 to 2, wherein the amount of oxygen and glycerol is (1.1 to 2): 1.
7. The separation method according to any one of claims 1-2, characterized in that the mass ratio of oxygen to glycerol is 1.2:1.
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| CN113956150A (en) * | 2020-07-21 | 2022-01-21 | 中国石油大学(华东) | Preparation method of glyceric acid |
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| Title |
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| Coproducing Value-Added Chemicals and Hydrogen with Electrocatalytic Glycerol Oxidation Technology: Experimental and Techno-Economic Investigations;Hyung Ju Kim et al.;《ACS Sustainable Chem. Eng.》;第5卷(第8期);第6626-6634页 * |
| Synergistic effects of bimetallic PtRu/MCM-41 nanocatalysts for glycerol oxidation in base-free medium: Structure and electronic coupling dependent activity;Hao Yan et al.;《Applied Catalysis B: Environmental》;第259卷;第118070 -118080页 * |
| 王基铭，袁晴棠主编.《石油化工技术进展》.中国石化出版社,2002,第660-661页. * |
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