CN115010687A - Demulsifier, preparation method thereof and vanillin extraction process - Google Patents
Demulsifier, preparation method thereof and vanillin extraction process Download PDFInfo
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- CN115010687A CN115010687A CN202210670317.0A CN202210670317A CN115010687A CN 115010687 A CN115010687 A CN 115010687A CN 202210670317 A CN202210670317 A CN 202210670317A CN 115010687 A CN115010687 A CN 115010687A
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- acid
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- aldehyde
- demulsifier
- vanillin
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- 238000000605 extraction Methods 0.000 title claims abstract description 82
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 235000012141 vanillin Nutrition 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000006114 decarboxylation reaction Methods 0.000 claims abstract description 43
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 24
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 claims description 19
- -1 4-bromo-2-hydroxybenzaldehyde compound Chemical class 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 claims description 19
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 19
- 229960002510 mandelic acid Drugs 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- CGQCWMIAEPEHNQ-UHFFFAOYSA-N Vanillylmandelic acid Chemical compound COC1=CC(C(O)C(O)=O)=CC=C1O CGQCWMIAEPEHNQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 10
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 4
- 239000001639 calcium acetate Substances 0.000 claims description 4
- 235000011092 calcium acetate Nutrition 0.000 claims description 4
- 229960005147 calcium acetate Drugs 0.000 claims description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 238000006277 sulfonation reaction Methods 0.000 claims description 2
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 description 17
- 239000003607 modifier Substances 0.000 description 12
- 238000007599 discharging Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 238000004945 emulsification Methods 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 5
- 239000002912 waste gas Substances 0.000 description 5
- XXDBEJYASPBHLS-UHFFFAOYSA-N 4-bromo-2-hydroxy-6-methylbenzaldehyde Chemical compound CC1=CC(Br)=CC(O)=C1C=O XXDBEJYASPBHLS-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 4
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- BRCUPBLSVSOLOM-UHFFFAOYSA-N (4-hydroxy-3-methoxyphenyl)-phenylmethanone Chemical compound C1=C(O)C(OC)=CC(C(=O)C=2C=CC=CC=2)=C1 BRCUPBLSVSOLOM-UHFFFAOYSA-N 0.000 description 2
- HXTWKHXDFATMSP-UHFFFAOYSA-N 4-bromo-2-hydroxybenzaldehyde Chemical compound OC1=CC(Br)=CC=C1C=O HXTWKHXDFATMSP-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N benzofuran Natural products C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960001867 guaiacol Drugs 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- 241001093501 Rutaceae Species 0.000 description 1
- 244000290333 Vanilla fragrans Species 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000015243 ice cream Nutrition 0.000 description 1
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N phenyl propionaldehyde Natural products CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/18—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted otherwise than in position 3 or 7
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
- B01D17/047—Breaking emulsions with separation aids
-
- 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
- C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a demulsifier, a preparation method thereof and an extraction process of vanillin, wherein the demulsifier has a structural formula as follows:
in the formula, R represents hydrogen or C1-C6 alkyl, decarboxylation and extraction are carried out in one reactor, oxidation reaction liquid, an extracting agent and acid liquid are respectively and continuously added from different positions of the reactor, and continuous decarboxylation and extraction are completed in the reactor.
Description
Technical Field
The invention belongs to the field of vanillin synthesis, and particularly relates to a demulsifier, a preparation method thereof and an extraction process of vanillin.
Background
Vanillin, also known as vanillin, chemical name 3-methoxy-4-hydroxybenzaldehyde, is an organic compound extracted from Vanilla planifolia of the family Rutaceae. As a common food flavoring agent, the product is widely applied to the fields of chocolate, milk powder, cakes, ice cream, toothpaste, perfume and the like.
At present, a process route of guaiacol and glyoxylic acid is mainly adopted for synthesizing vanillin, the process route comprises the steps of condensation, oxidation, decarboxylation extraction and the like, wherein the decarboxylation reaction is to carry out decarboxylation reaction on 3-methoxy-4-hydroxy-phenylketoacid generated in the last step of oxidation under the action of Lewis acid to generate vanillin and release carbon dioxide. At normal temperature, the solubility of vanillin in water is only 1%, and a large amount of generated vanillin is separated out from the reaction liquid and needs to be collected by adding an extracting agent. The existing decarboxylation process is divided into two processes of decarboxylation and extraction by adopting decarboxylation and extraction separately, namely, reaction liquid after decarboxylation is conveyed to an extraction device, and the process is an intermittent process and has two outstanding problems; firstly, vanillin separated out by decarboxylation is easy to solidify into a solid, so that the risk of blocking a pipeline is caused; secondly, a large number of emulsion layers can appear in the organic solvent extraction process, which causes great trouble for subsequent separation.
The decarboxylation reaction temperature is normal temperature, in order to solve the problem of decarboxylation reaction, the temperature of the decarboxylation reaction is increased to 60-65 ℃ by patent CN102010310A, although the risk of vanillin precipitation into solid can be effectively reduced, vanillin is a heat sensitive substance, and the yield of the decarboxylation reaction is low due to high temperature. Patent CN102190567A provides a process for eliminating an emulsion layer of decarboxylation extract, which comprises the steps of carrying out centrifugal separation on the emulsion layer, and adopting a mode of combining a sedimentation centrifuge and a tubular centrifuge to completely separate an organic phase, an insoluble copper salt and a water phase in the emulsion layer. Patent CN102276434A adds the vanillin that separates out in with the decarboxylation liquid and washes in the washing kettle, with the clear water many times, and the vanillin solid after the washing melts back and gets into the extraction process, can avoid the vanillin solid to separate out like this, can wash away impurity in advance again, reduces the appearance of emulsion layer, and nevertheless too much washing causes more waste water, and the energy consumption is higher.
Disclosure of Invention
The invention is an improvement of processes for preparing vanillin by condensation, oxidation, decarboxylation and extraction of guaiacol and glyoxylic acid, and aims to solve the defects of the prior invention, the invention provides a demulsifier and a preparation method thereof, which are used for extracting vanillin decarboxylation reaction liquid, can effectively avoid emulsification in the extraction process and improve the separation efficiency; the invention also provides a process for extracting vanillin.
In order to solve the problems, the invention provides a demulsifier, which has the structural formula:
wherein R represents hydrogen or C1-C6 alkyl.
The invention also provides a preparation method of the demulsifier, which comprises the following steps:
(1) carrying out sulfonation reaction on the 4-bromo-2-hydroxybenzaldehyde compound and sulfuric acid to obtain a 2-bromo-5-aldehyde-4-hydroxybenzenesulfonic acid compound;
(2) butyl lithium is dripped into the 2-bromo-5-aldehyde-4-hydroxybenzene sulfonic acid compound, and then the butyl lithium reacts with triethylamine to generate the 2- (diethylamino) -5-aldehyde-4-hydroxybenzene sulfonic acid compound.
(3) Reacting the 2- (diethylamino) -5-aldehyde-4-hydroxybenzene sulfonic acid compound with acetic anhydride under the action of a catalyst to obtain the demulsifier.
Wherein the structural formula of the 4-bromo-2-hydroxybenzaldehyde compound is as follows:
r represents hydrogen or C1-C6 alkyl.
Said 2-bromo-The structural formula of the 5-aldehyde-4-hydroxybenzene sulfonic acid compound is as follows:
r represents hydrogen or C1-C6 alkyl.
The structural formula of the 2- (diethylamino) -5-aldehyde-4-hydroxybenzene sulfonic acid compound is as follows:
wherein R represents hydrogen or C1-C6 alkyl.
The synthetic route of the demulsifier is shown as follows:
the step (1) of the present invention may be carried out at normal temperature and pressure.
Step (1) of the present invention may be performed in a solvent a comprising at least one of water, acetone, DMF, DMAC, and DMSO, preferably DMF or water.
In the step (1), the mass ratio of the 4-bromo-2-hydroxybenzaldehyde compound to the solvent A is 1 (3-10), preferably 1 (5-8).
The sulfuric acid in the step (1) of the invention is fuming sulfuric acid or 98% concentrated sulfuric acid.
In the step (1) of the present invention, the mass ratio of the 4-bromo-2-hydroxybenzaldehyde compound to the sulfuric acid is 1 (1.5-4), preferably 1 (2-3).
The reaction time in the step (1) is 1-8 h, preferably 3-5 h.
Step (2) of the present invention may be carried out in a solvent B comprising one or more of toluene, ethylbenzene, tetrahydrofuran, DMF and diethyl ether, preferably toluene or tetrahydrofuran.
In the step (2), the mass ratio of the 2-bromo-5-formyl-4-hydroxybenzenesulfonic acid compound to the solvent B is 1 (3-10), preferably 1 (5-8).
In the step (2), the mass ratio of the 2-bromo-5-formyl-4-hydroxybenzenesulfonic acid compound to the butyllithium is (2-4): 1, preferably (2.5-3): 1; the mass ratio of triethylamine to the 2-bromo-5-aldehyde-4-hydroxybenzenesulfonic acid compound is (1-4): 1, preferably (2-3): 1.
the reaction conditions in the step (2) are anhydrous and anaerobic environments.
In the step (2), the initial reaction stage is the butyl lithium dripping stage, the reaction temperature is-100-0 ℃, acetone bath is carried out, triethylamine is added after the butyl lithium is dripped, the temperature is slowly raised to the room temperature, and the reaction is continued.
The reaction time of the step (2) is 3-8 h, and the preferable reaction time is 4-6 h.
The post-treatment mode of the step (2) of the invention is as follows: adding deionized water to quench unreacted butyl lithium, and then adding a solvent to perform extraction to obtain a crude product, wherein the preferred extraction solvent is n-hexane or petroleum ether.
The solvent selected in the step (3) is DMF, and the mass ratio of DMF to the 2- (diethylamino) -5-aldehyde-4-hydroxybenzene sulfonic acid compound is (3-15): 1, preferably (5-10): 1.
in the step (3), the catalyst is one or more of sodium acetate, calcium acetate and potassium acetate, and the mass ratio of the 2- (diethylamino) -5-aldehyde-4-hydroxybenzene sulfonic acid compound to the catalyst is (10-50): 1, preferably (20-30): 1.
in the step (3), the mass ratio of acetic anhydride to 2- (diethylamino) -5-aldehyde-4-hydroxybenzenesulfonic acid is (4-10): 1, preferably (5-8): 1.
the reaction temperature in the step (3) is 100-200 ℃, and the preferable reaction temperature is 120-140 ℃.
The reaction time of the step (3) is 0.1-2 h, preferably 0.5-1 h.
The invention relates to a process for extracting vanillin, which is added with the demulsifier.
In the vanillin extraction process, the solution to be extracted is a reaction solution obtained after oxidation and decarboxylation of mandelic acid. Extracting vanillin in reaction liquid by using an extractant, wherein a demulsifier is added in the reaction liquid.
Preferably, the mass ratio of the added amount of the demulsifier to the mandelic acid oxidation reaction liquid is 0.01-0.05.
A process for extracting vanillin includes such steps as continuously adding the oxidizing reaction liquid of mandelic acid, acid liquid, demulsifier and extractant to reactor, feeding the oxidizing reaction liquid of mandelic acid from the top of reactor, feeding extractant from the bottom of reactor, and extracting the oxidizing reaction liquid of mandelic acid by contact.
Preferably, the feed rate ratio of the extractant to the mandelic acid oxidation reaction liquid is 1: 3-1: 10.
in the invention, decarboxylation and extraction can be combined into one, the extractant and the mandelic acid oxidation reaction liquid can be continuously injected into a reactor, the acid liquid and the 3-methoxy-4-hydroxyphenylketo acid in the mandelic acid oxidation reaction liquid are subjected to decarboxylation, the generated vanillin is recovered by the extractant, and the continuous decarboxylation and the continuous extraction can be realized in one reactor.
The reactor of the invention can be selected from a reaction kettle with stirring, a plate-type extraction tower, a rotary disc extraction tower, a Cheney extraction tower and the like, and is preferably a rotary disc extraction tower. The uppermost end of the reactor is provided with an exhaust hole, and the reactor can be shaped into a cylinder with a thin middle part and thick two ends for better standing and layering.
The mandelic acid oxidation reaction solution is intermediate reaction solution for vanillin synthesis, and is obtained by oxidizing 3-methoxy-4-hydroxymandelic acid serving as a raw material, and the reaction solution mainly comprises 70-90 wt% of water, 5-15 wt% of 3-methoxy-4-hydroxyphenylketo acid and 5-8 wt% of sodium sulfate. The extractant is selected from one or more of toluene, ethyl acetate, butyl acetate, n-hexane, anisole, methyl isobutyl ketone and acetophenone, and the preferred extractant is methyl isobutyl ketone or toluene.
The demulsifier and the acid liquor are fed from the upper part of the reactor, the demulsifier and the acid liquor can be mixed firstly and then continuously added from the top of the reactor, the acid liquor adopts one or more of dilute hydrochloric acid, dilute sulfuric acid and dilute nitric acid, the concentration is 5-30%, and the mass ratio of the acid liquor to the reaction liquid is 1: 10 to 20.
The invention has the beneficial effects that:
the invention provides a novel demulsifier 6-sulfo-7- (diethylamino) benzofuran for extraction, which takes coumarin as a main body and has a similar main body structure with impurities in vanillin, so that the same post-treatment process is conveniently adopted in the later period, and sulfonic groups and quaternary ammonium functional groups are introduced, so that the solubility and demulsification capability of the material in water are respectively enhanced, and the separation of an extractant and vanillin reaction liquid is better realized.
The invention also provides a process for extracting vanillin, by adopting the demulsifier, the decarboxylation and the extraction can be completed in one reactor, the continuous operation can be carried out, the operation is simple, the process flow is optimized, and the problems of complicated operation, vanillin precipitation and the like in the conventional intermittent decarboxylation and intermittent extraction are avoided.
Drawings
FIG. 1 is a schematic diagram of the continuous decarboxylation and extraction reaction process of the present invention.
Detailed Description
The method according to the invention will be further illustrated by the following examples, but the invention is not limited to the examples listed, but also encompasses any other known modification within the scope of the claims of the invention.
The raw material sources are as follows:
4-bromo-2-hydroxybenzaldehyde, Shanghai Michelin Biochemical technology Ltd;
4-bromo-2-hydroxy-6-methylbenzaldehyde, Shanghai Xin Yuan pharmaceutical science and technology, Inc.
Example 1
40g of 4-bromo-2-hydroxybenzaldehyde and 140g of DMF are injected into a three-neck flask, then 64g of concentrated sulfuric acid (98%) is slowly dripped, reaction is continued for 1.5h after the dripping is finished, and 2-bromo-5-aldehyde-4-hydroxybenzenesulfonic acid is obtained by separation and purification. 40g of 2-bromine-5-aldehyde-4-hydroxybenzenesulfonic acid and 125g of toluene are injected into an anhydrous oxygen-free glass bottle, 20g of butyllithium (1mol/L) is slowly dropped into the reaction system at-78 ℃, then 40g of triethylamine is added, the temperature is raised to room temperature, the reaction is continued for 4 hours, and the 2- (diethylamino) -5-aldehyde-4-hydroxybenzenesulfonic acid is obtained after separation and purification. 40g of 2- (diethylamino) -5-aldehyde-4-hydroxybenzenesulfonic acid, 160g of acetic anhydride and 4g of sodium acetate are dissolved in DMF, and the mixture is heated to 120 ℃ to react for 40min to obtain the extraction modifier 6-sulfo-7- (diethylamino) benzofuran.
Referring to FIG. 1, a reaction solution obtained by oxidizing 3-methoxy-4-hydroxymandelic acid (85 wt% of water, 9 wt% of 3-methoxy-4-hydroxyphenylketo acid, 6 wt% of sodium sulfate) was continuously fed at 1kg/h from the upper end of a rotating disk extraction tower, toluene was continuously fed at 0.33kg/h from the bottom of the rotating disk extraction tower, 6-sulfo-7- (diethylamino) benzofuran as an extraction modifier and a dilute sulfuric acid solution mixture (5: 95 by mass of the extraction modifier and 30 wt% of dilute sulfuric acid) were continuously fed at 200g/h from the top of the rotating disk extraction tower, decarboxylation and extraction are carried out in the rotary disc extraction tower, waste gas generated by decarboxylation is discharged from an exhaust hole at the top, vanillin generated by reaction is extracted by toluene and is discharged from the top of the rotary disc extraction tower for rectification and separation. No significant emulsification was found throughout the decarboxylation and extraction process, with the water-oil interfacial zone (not completely separated zone) accounting for approximately 2% of the total volume of the rotating disk column.
Example 2
60g of 4-bromo-2-hydroxy-6-methylbenzaldehyde and 480g of DMAC are injected into a three-necked bottle, then 180g of concentrated sulfuric acid (98%) is slowly dripped, reaction is continued for 3 hours after the dripping is finished, and the 2-bromo-4-hydroxy-5-aldehyde-6-methyl benzenesulfonic acid is obtained through separation and purification. 40g of 2-bromine-4-hydroxy-5-aldehyde-6-methylbenzenesulfonic acid and 120g of tetrahydrofuran are injected into an anhydrous oxygen-free glass bottle, 17g of butyllithium (1mol/L) is slowly dropped into a reaction system at-78 ℃, then 80g of triethylamine is added, the temperature is raised to room temperature, the reaction is continued for 6 hours, and the 2- (diethylamino) -4-hydroxy-5-aldehyde-6-ethylbenzenesulfonic acid is obtained after separation and purification. 40g of 2- (diethylamino) -4-hydroxy-5-aldehyde-6-methylbenzenesulfonic acid, 360g of acetic anhydride and 2g of calcium acetate are dissolved in DMF, and the mixture is heated to 160 ℃ to react for 30min to obtain the extraction modifier 5-methyl-6-sulfonic-7- (diethylamino) benzofuran.
Continuously adding reaction liquid (85 wt% of water, 9 wt% of 3-methoxy-4-hydroxybenzophenone and 6 wt% of sodium sulfate) obtained after oxidation of 3-methoxy-4-hydroxymandelic acid from the upper end of a rotating disc extraction tower at a ratio of 1kg/h, continuously adding methyl isobutyl ketone from the bottom of a plate-type extraction tower at a ratio of 0.2kg/h, continuously adding 5-methyl-6-sulfo-7- (diethylamino) benzofuran serving as an extraction modifier and a dilute acid liquid mixture (the mass ratio of the extraction modifier to 30 wt% of dilute sulfuric acid is 1: 9) into the rotating disc extraction tower from the top at a speed of 200g/h, performing decarboxylation and extraction in the rotating disc extraction tower, discharging waste gas generated by decarboxylation from a vent hole at the top, extracting vanillin generated by the reaction with methyl isobutyl ketone, and discharging from the top of the rotating disc extraction tower, and (5) performing rectification separation. No significant emulsification was found throughout the decarboxylation and extraction process, with the water-oil interfacial zone (not completely separated zone) accounting for approximately 2% of the total volume of the rotating disk column.
Example 3
40g of 4-bromo-2-hydroxy-6-methylbenzaldehyde and 150g of water are injected into a three-necked bottle, 65g of concentrated sulfuric acid (98%) is slowly dripped, reaction is continued for 5 hours after the dripping is finished, and 2-bromo-4-hydroxy-5-aldehyde-6-methylbenzenesulfonic acid is obtained through separation and purification. 40g of 2-bromine-4-hydroxy-5-aldehyde-6-methylbenzenesulfonic acid and 160g of DMF are injected into an anhydrous oxygen-free glass bottle, 10g of butyllithium (1mol/L) is slowly dropped into the reaction system at-78 ℃, then 100g of triethylamine is added, the temperature is raised to room temperature, the reaction is continued for 3.5 hours, and the 2- (diethylamino) -4-hydroxy-5-aldehyde-6-methylbenzenesulfonic acid is obtained after separation and purification. 40g of 2- (diethylamino) -4-hydroxy-5-aldehyde-6-methylbenzenesulfonic acid, 160g of acetic anhydride and 1g of potassium acetate are dissolved in DMF, and the mixture is heated to 110 ℃ to react for 20min to obtain the extraction modifier 5-methyl-6-sulfonic-7- (diethylamino) benzofuran.
Continuously adding reaction liquid (85 wt% of water, 9 wt% of 3-methoxy-4-hydroxyphenylketo acid and 6 wt% of sodium sulfate) obtained after the oxidation of 3-methoxy-4-hydroxymandelic acid into a rotary disc extraction tower at a ratio of 1kg/h, continuously adding butyl acetate into the rotary disc extraction tower at a ratio of 0.15kg/h, continuously adding 5-methyl-6-sulfo-7- (diethylamino) benzofuran serving as an extraction modifier and a dilute acid liquid mixture (the mass ratio of the extraction modifier to 30 wt% of dilute sulfuric acid is 15: 85) into the rotary disc extraction tower at a speed of 300g/h, performing decarboxylation and extraction in the rotary disc extraction tower, discharging waste gas generated by decarboxylation from a vent hole at the top, extracting vanillin generated by the reaction by butyl acetate, and discharging from the top of the rotary disc extraction tower, and (5) performing rectification separation. No significant emulsification was found throughout the decarboxylation and extraction process, with the water-oil interfacial zone (not completely separated zone) accounting for approximately 2% of the total volume of the rotating disk column.
Example 4
40g of 4-bromo-2-hydroxy-6-methylbenzaldehyde and 200g of DMF are injected into a three-necked flask, then 120g of concentrated sulfuric acid (98%) is slowly dripped, reaction is continued for 2.8h after the dripping is finished, and separation and purification are carried out to obtain the 2-bromo-4-hydroxy-5-aldehyde-6-methylbenzenesulfonic acid. 42g of 2-bromo-4-hydroxy-5-aldehyde-6-methylbenzenesulfonic acid and 120g of tetrahydrofuran are injected into an anhydrous oxygen-free glass bottle, 16g of butyllithium (1mol/L) is slowly dropped into the reaction system at-78 ℃, then 90g of triethylamine is added, the temperature is raised to room temperature, the reaction is continued for 5 hours, and the 2- (diethylamino) -4-hydroxy-5-aldehyde-6-methylbenzenesulfonic acid is obtained after separation and purification. 40g of 2- (diethylamino) -4-hydroxy-5-formyl-6-methylbenzenesulfonic acid, 200g of acetic anhydride and 1.8g of calcium acetate are dissolved in DMF, and the mixture is heated to 180 ℃ to react for 30min to obtain the extraction modifier 5-methyl-6-sulfo-7- (diethylamino) benzofuran.
Continuously adding reaction liquid (85 wt% of water, 9 wt% of 3-methoxy-4-hydroxybenzophenone and 6 wt% of sodium sulfate) obtained after oxidation of 3-methoxy-4-hydroxymandelic acid from the upper end of a rotating disc extraction tower at a ratio of 1kg/h, continuously adding methyl isobutyl ketone from the bottom of a plate-type extraction tower at a ratio of 0.2kg/h, continuously adding 5-methyl-6-sulfo-7- (diethylamino) benzofuran serving as an extraction modifier and a dilute acid liquid mixture (the mass ratio of the extraction modifier to 30 wt% of dilute sulfuric acid is 1: 9) into the rotating disc extraction tower from the top at a speed of 200g/h, performing decarboxylation and extraction in the rotating disc extraction tower, discharging waste gas generated by decarboxylation from a vent hole at the top, extracting vanillin generated by the reaction with methyl isobutyl ketone, and discharging from the top of the rotating disc extraction tower, and (5) performing rectification separation. No significant emulsification was found throughout the decarboxylation and extraction process, with the water-oil interfacial zone (not completely separated zone) accounting for approximately 2% of the total volume of the rotating disk column.
Comparative example 1
Continuously adding reaction liquid (85 wt% of water, 9 wt% of 3-methoxy-4-hydroxyphenylketo acid and 6 wt% of sodium sulfate) obtained after the oxidation of 3-methoxy-4-hydroxymandelic acid from the upper end of a rotary disc extraction tower at a speed of 1kg/h, continuously adding methyl isobutyl ketone from the bottom of a plate type extraction tower at a speed of 0.2kg/h, continuously adding 30% dilute acid liquid into the rotary disc extraction tower from the top at a speed of 200g/h, performing decarboxylation and extraction in the rotary disc extraction tower, discharging waste gas generated by decarboxylation from a vent hole at the top, extracting vanillin generated by the reaction by methyl isobutyl ketone, discharging the vanillin from the top of the rotary disc extraction tower, and performing rectification separation. Significant emulsification was found throughout the extraction process, with the water-oil interfacial zone (not completely separated zone) accounting for approximately 20% of the total volume of the rotating disk column.
Claims (10)
1. A demulsifier, characterized in that it has the structural formula:
wherein R represents hydrogen or C1-C6 alkyl.
2. The method for preparing the demulsifier of claim 1, which comprises the following steps:
(1) carrying out sulfonation reaction on the 4-bromo-2-hydroxybenzaldehyde compound and sulfuric acid to obtain a 2-bromo-5-aldehyde-4-hydroxybenzenesulfonic acid compound;
(2) butyl lithium is dripped into the 2-bromo-5-aldehyde-4-hydroxybenzenesulfonic acid compound, and then the butyl lithium reacts with triethylamine to generate the 2- (diethylamino) -5-aldehyde-4-hydroxybenzenesulfonic acid compound;
(3) reacting the 2- (diethylamino) -5-aldehyde-4-hydroxybenzene sulfonic acid compound with acetic anhydride under the action of a catalyst to obtain the demulsifier.
3. The method according to claim 2, wherein the structural formula of the 4-bromo-2-hydroxybenzaldehyde compound is:
r represents hydrogen or C1-C6 alkyl;
the 2-bromo-5-aldehyde-4-hydroxyThe structural formula of the radical benzenesulfonic acid compound is as follows:
r represents hydrogen or C1-C6 alkyl;
the structural formula of the 2- (diethylamino) -5-aldehyde-4-hydroxybenzene sulfonic acid compound is as follows:
wherein R represents hydrogen or C1-C6 alkyl.
4. The method according to claim 2 or 3, wherein the step (1) is carried out in a solvent A comprising at least one of water, acetone, DMF, DMAC and DMSO, preferably DMF or water;
preferably, in the step (1), the mass ratio of the 4-bromo-2-hydroxybenzaldehyde compound to the solvent A is 1 (3-10), preferably 1 (5-8);
preferably, the sulfuric acid in step (1) is selected from fuming sulfuric acid or 98% concentrated sulfuric acid;
preferably, the reaction time in the step (1) is 1-8 hours, preferably 3-5 hours;
preferably, in the step (1), the mass ratio of the 4-bromo-2-hydroxybenzaldehyde compound to the sulfuric acid is 1 (1.5-4), preferably 1 (2-3).
5. The method according to any one of claims 2 to 4, wherein the step (2) is carried out in a solvent B comprising one or more of toluene, ethylbenzene, tetrahydrofuran, DMF and diethyl ether, preferably toluene or tetrahydrofuran;
preferably, in the step (2), the mass ratio of the 2-bromo-5-aldehyde-4-hydroxybenzenesulfonic acid compound to the solvent B is 1 (3-10), preferably 1 (5-8);
preferably, in the step (2), the mass ratio of the 2-bromo-5-aldehyde-4-hydroxybenzenesulfonic acid compound to the butyllithium is (2-4): 1, preferably (2.5-3): 1;
preferably, the mass ratio of triethylamine to the 2-bromo-5-aldehyde-4-hydroxybenzenesulfonic acid compound is (1-4): 1, preferably (2-3): 1;
preferably, the reaction conditions in the step (2) are an anhydrous and oxygen-free environment;
preferably, the initial reaction stage in the step (2) is a butyl lithium dripping stage, the reaction temperature is-100-0 ℃, acetone bath is carried out, triethylamine is added after the butyl lithium is dripped, the temperature is slowly raised to the room temperature, and the reaction is continued;
preferably, the reaction time of the step (2) is 3-8 h, and the preferred reaction time is 4-6 h;
preferably, the post-treatment manner of step (2) is: adding deionized water to quench unreacted butyl lithium, and then adding a solvent to perform extraction to obtain a crude product, wherein the preferable extraction solvent is n-hexane or petroleum ether.
6. The preparation method according to any one of claims 2 to 5, wherein the solvent used in the step (3) is DMF, and the mass ratio of DMF to the 2- (diethylamino) -5-aldehyde-4-hydroxybenzenesulfonic acid compound is (3-15): 1, preferably (5-10): 1;
preferably, in the step (3), the catalyst is one or more of sodium acetate, calcium acetate and potassium acetate, and the mass ratio of the 2- (diethylamino) -5-aldehyde-4-hydroxybenzene sulfonic acid compound to the catalyst is (10-50): 1, preferably (20-30): 1;
preferably, the mass ratio of acetic anhydride to 2- (diethylamino) -5-aldehyde-4-hydroxybenzenesulfonic acid in the step (3) is (4-10): 1, preferably (5-8): 1;
preferably, the reaction temperature in the step (3) is 100-200 ℃, and the reaction temperature is preferably 120-140 ℃;
preferably, the reaction time in the step (3) is 0.1-2 h, preferably 0.5-1 h.
7. An extraction process of vanillin, wherein the demulsifier of claim 1 or the demulsifier prepared by the preparation method of any one of claims 2-6 is added in the extraction process;
in the vanillin extraction process, the solution to be extracted is a reaction solution obtained after oxidation and decarboxylation of mandelic acid;
preferably, an extractant is used for extracting vanillin in the reaction liquid, wherein a demulsifier is added in the reaction liquid;
preferably, the mass ratio of the added amount of the demulsifier to the mandelic acid oxidation reaction liquid is 0.01-0.05.
8. The process for extracting vanillin of claim 7, wherein mandelic acid oxidation reaction liquid, the acid solution, the demulsifier and the extractant are continuously added into the reactor, the mandelic acid oxidation reaction liquid is fed from the upper part of the reactor, the extractant is fed from the lower end of the reactor, and the extractant and the mandelic acid oxidation reaction liquid are discharged from the upper part of the reactor after being contacted and extracted in the reactor;
preferably, the feed rate ratio of the extractant to the mandelic acid oxidation reaction liquid is 1: 3-1: 10.
9. the vanillin extraction process according to claim 7, wherein the decarboxylation and extraction of the mandelic acid oxidation reaction solution are combined into one, an extractant and the mandelic acid oxidation reaction solution are continuously injected into a reactor, the acid solution and 3-methoxy-4-hydroxyphenylketo acid in the mandelic acid oxidation reaction solution undergo a decarboxylation reaction, the generated vanillin is recovered by the extractant, and the continuous decarboxylation and continuous extraction are realized in one reactor;
preferably, the mandelic acid oxidation reaction solution is an intermediate reaction solution for vanillin synthesis, and is a reaction solution obtained by oxidizing 3-methoxy-4-hydroxymandelic acid serving as a raw material, wherein the reaction solution mainly comprises 70-90 wt% of water, 5-15 wt% of 3-methoxy-4-hydroxyphenylketo acid and 5-8 wt% of sodium sulfate;
preferably, the demulsifier and the acid solution are fed from the upper part of the reactor, the demulsifier and the acid solution can be mixed firstly and then continuously added from the top of the reactor, the acid solution is one or more of dilute hydrochloric acid, dilute sulfuric acid and dilute nitric acid, the concentration of the acid solution is 5-30%, and the mass ratio of the acid solution to the reaction solution is 1: 10 to 20.
10. Vanillin extraction process according to any of claims 7-9, the extractant being selected from one or more of toluene, ethyl acetate, butyl acetate, n-hexane, anisole, methyl isobutyl ketone, acetophenone, preferably methyl isobutyl ketone or toluene.
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