CN117720407A - Waste residue treatment method - Google Patents
Waste residue treatment method Download PDFInfo
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- CN117720407A CN117720407A CN202311721540.4A CN202311721540A CN117720407A CN 117720407 A CN117720407 A CN 117720407A CN 202311721540 A CN202311721540 A CN 202311721540A CN 117720407 A CN117720407 A CN 117720407A
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- sorbitol
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- 239000002699 waste material Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 claims abstract description 18
- 229940087101 dibenzylidene sorbitol Drugs 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000002253 acid Chemical class 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 44
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 24
- 239000000600 sorbitol Substances 0.000 claims description 24
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 22
- 239000007795 chemical reaction product Substances 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 150000007513 acids Chemical class 0.000 claims description 9
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- POQJHLBMLVTHAU-UHFFFAOYSA-N 3,4-Dimethylbenzaldehyde Chemical compound CC1=CC=C(C=O)C=C1C POQJHLBMLVTHAU-UHFFFAOYSA-N 0.000 claims description 5
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 5
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 5
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003934 aromatic aldehydes Chemical class 0.000 abstract description 23
- 210000003298 dental enamel Anatomy 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- -1 sorbitol acetal compound Chemical class 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 239000012263 liquid product Substances 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- 150000002373 hemiacetals Chemical class 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 150000001241 acetals Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- DKBCURTUXYMRFB-LXTVHRRPSA-N (2r,3r,4s,5r)-7-(3,4-dimethylphenyl)hept-6-ene-1,2,3,4,5,6-hexol Chemical compound CC1=CC=C(C=C(O)[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO)C=C1C DKBCURTUXYMRFB-LXTVHRRPSA-N 0.000 description 2
- HZVFRKSYUGFFEJ-YVECIDJPSA-N (2r,3r,4s,5r)-7-phenylhept-6-ene-1,2,3,4,5,6-hexol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=CC1=CC=CC=C1 HZVFRKSYUGFFEJ-YVECIDJPSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- YWEWWNPYDDHZDI-JJKKTNRVSA-N (1r)-1-[(4r,4ar,8as)-2,6-bis(3,4-dimethylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C1=C(C)C(C)=CC=C1C1O[C@H]2[C@@H]([C@H](O)CO)OC(C=3C=C(C)C(C)=CC=3)O[C@H]2CO1 YWEWWNPYDDHZDI-JJKKTNRVSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 229940053991 aldehydes and derivative Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a waste residue treatment method. The treatment method of the invention comprises the following steps: reacting an initial reaction system containing waste residues, 150-650 parts by volume of monohydric alcohol, acid compounds and 700-1300 parts by volume of water for 0.5-3 hours, then adding 300-500 parts by volume of water into the reaction system, and continuing the reaction; wherein the mass volume ratio of the waste residue to the monohydric alcohol is (250-800): 150-650 kg/L; the waste residue is from the production process of dibenzylidene sorbitol. The method can fully recover aromatic aldehydes.
Description
Technical Field
The invention relates to a waste residue treatment method, in particular to a waste residue treatment method generated in the dibenzylidene sorbitol production process.
Background
The transparent sorbitol nucleating agent is one kind of polyolefin product modifying assistant with relatively wide application, and has the synthesis process of condensation reaction of sorbitol and aromatic aldehyde in the presence of solvent and acid catalyst to obtain dibenzylidene sorbitol and side product. The by-products are typically tribenzylidene sorbitol (polyacetal) and monobenzylidene sorbitol (hemi-acetal). The condensation reactant obtained by the method needs to be separated from the solid crude product and the solvent by a filter press, and most of impurities and a small part of products (dibenzylidene sorbitol) can enter the solvent system, so that the pollution of the solvent system and the yield of the yield are reduced. These impurities include unreacted starting materials, byproducts, and salts resulting from neutralization of the acid and base. In order to recover the product in the solvent system, the solvent mother liquor obtained by filter pressing needs to be subjected to rapid distillation to separate out impurities and the product, and then the product in the precipitate is separated out. Since the precipitate contains a large amount of readily soluble hemiacetals and they are coked during distillation, the product cannot be taken out by washing. This greatly affects the utilization rate of raw materials and the yield of products.
CN114933521a discloses a process for recovering and reproducing aromatic aldehyde, which is applied to the treatment of waste liquid from the preparation of sorbitol acetal compound nucleating agent. Presetting a static extraction device, putting water with a preset height into the extraction device, and putting extractant with a preset height into the extraction device to form a lower water layer and an upper extractant layer; introducing the waste liquid containing aromatic aldehyde from the top of the extraction device to the upper surface of the extractant layer, and allowing the waste liquid to enter the lower water layer through the extractant layer, so that the aromatic aldehyde in the waste liquid is absorbed by the extractant to form an extraction phase; when the concentration of the aromatic aldehyde in the extraction phase reaches more than 18%, the extraction phase is taken out for preparing the sorbitol acetal compound nucleating agent again, and the process flow of recycling and reproducing the aromatic aldehyde once is completed. The method can only recover the aromatic aldehyde which does not participate in the reaction, but the product and the byproducts in the waste liquid cannot be recovered.
Disclosure of Invention
Accordingly, the present invention has been made in view of the above problems occurring in the prior art, and an object of the present invention is to provide a method for treating waste residues, which can sufficiently hydrolyze acetals and hemi-acetals in waste residues generated in the process of producing dibenzylidene sorbitol into aromatic aldehydes, thereby sufficiently recovering the aromatic aldehydes, and greatly improving the utilization ratio of raw materials of aromatic aldehydes to be fed in the process of producing dibenzylidene sorbitol.
The above object is achieved by the following technical scheme.
The invention provides a treatment method of waste residues, wherein the waste residues are from the production process of dibenzylidene sorbitol;
the method comprises the following steps: reacting an initial reaction system containing waste residues, 150-650 parts by volume of monohydric alcohol, acid compounds and 700-1300 parts by volume of water for 0.5-3 hours, then adding 300-500 parts by volume of water into the reaction system, and continuing the reaction;
wherein the mass volume ratio of the waste residue to the monohydric alcohol is (250-800): 150-650 kg/L.
According to the treatment method of the present invention, preferably, the waste residue contains sorbitol, benzaldehyde and its derivatives represented by formula (I), monobenzyl sorbitol formed by benzaldehyde and its derivatives represented by formula (I) and sorbitol, dibenzylidene sorbitol formed by benzaldehyde and its derivatives represented by formula (I) and sorbitol, and tribenzyl sorbitol formed by benzaldehyde and its derivatives represented by formula (I) and sorbitol;
in the formula (I), R 1 And R is 2 Independently selected from H, C to C6 alkyl groups.
According to the treatment method of the present invention, preferably, the benzaldehyde and its derivative are selected from one or more of 3, 4-dimethylbenzaldehyde, benzaldehyde, and p-methylbenzaldehyde.
According to the treatment method of the present invention, preferably, the mass ratio of the waste residue to the acidic compound is (250 to 800): (1-10).
According to the treatment method of the present invention, preferably, the monohydric alcohol is an aliphatic monohydric alcohol having 1 to 6 carbon atoms, and the acidic compound is selected from sulfuric acid, hydrochloric acid, benzenesulfonic acid represented by formula (II) and derivatives thereof;
in the formula (II), R 3 And R is 4 Independently selected from H, C to C6 alkyl groups.
According to the treatment method of the present invention, preferably, the monohydric alcohol is an aliphatic monohydric alcohol having 1 to 3 carbon atoms, R 3 And R is 4 Independently selected from H, C to C3 alkyl groups.
According to the treatment method of the present invention, preferably, the initial reaction system is reacted at 60 to 95℃and the reaction is continued at 60 to 95℃for 0.5 to 3 hours after the addition of water.
According to the treatment method of the present invention, it is preferable that water is added to the reaction system at a flow rate of 100 to 300L/h.
According to the treatment method of the present invention, preferably, the waste residue, the monohydric alcohol and the acidic compound are mixed to obtain a mixture; water was added to the mixture at the reaction temperature to form an initial reaction system.
The treatment method according to the present invention preferably further comprises the steps of:
and (3) standing and layering a reaction product obtained by continuing the reaction after adding water, rectifying and purifying the oil phase to obtain benzaldehyde and derivatives thereof.
The treatment method can fully hydrolyze acetal and hemiacetal substances in waste residues generated in the dibenzylidene sorbitol production process into aromatic aldehyde substances, fully recover the aromatic aldehyde substances, and greatly improve the utilization rate of the aromatic aldehyde substance raw materials for producing dibenzylidene sorbitol. Furthermore, the treatment method disclosed by the invention is simple in process, suitable for industrial production, and high in purity of the recovered aromatic aldehyde substances.
Detailed Description
The present invention will be further described with reference to specific examples, but the scope of the present invention is not limited thereto.
The treatment method of the waste residue comprises the following steps: the initial reaction system containing waste residue, monohydric alcohol, acid compound and water is reacted for 0.5-3 h, then water is added into the reaction system to continue the reaction.
The waste residue of the invention is from the production process of dibenzylidene sorbitol. Concretely, sorbitol and aromatic aldehyde substances are subjected to condensation reaction in the presence of an acid catalyst and a solvent to obtain a reaction product. And (3) carrying out filter pressing and washing on the reaction product to obtain a solid crude product and a solvent system. Distilling the solvent system to obtain waste residue.
The aromatic aldehyde and the derivative thereof have a structure shown in a formula (I):
in the formula (I), R 1 And R is 2 Alkyl groups each independently selected from H, C to C6; preferably, R 1 And R is 2 Alkyl groups each independently selected from H, C to C3; more preferably, R 1 And R is 2 Each independently selected from H, methyl.
R 2 May be located ortho or meta to the aldehyde group.
Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, methylpropyl, pentyl, methylbutyl, dimethylpropyl, ethylpropyl, hexyl, methylpentyl, dimethylbutyl, ethylbutyl.
In certain embodiments, the aromatic aldehyde and derivatives thereof are selected from one or more of 3, 4-dimethylbenzaldehyde, benzaldehyde, p-methylbenzaldehyde.
In certain embodiments, dibenzylidene sorbitol is selected from one or more of 1,3:2, 4-bis (3, 4-dimethylbenzylidene) sorbitol, 1,3:2, 4-dibenzylidene sorbitol, 1,3:2, 4-bis (paramethylbenzylidene) sorbitol.
The waste residue may contain unreacted raw materials, byproducts and target products. In certain embodiments, salts resulting from acid-base neutralization may also be included.
Unreacted starting materials include sorbitol, aromatic aldehydes and derivatives thereof. The aromatic aldehyde and its derivatives are specifically shown in the foregoing, and will not be described herein.
The unreacted raw materials may be contained in the waste residue in an amount of 1 to 10wt%. In certain embodiments, the unreacted starting materials are present in the waste residue in an amount of 3 to 7wt%.
Byproducts include monobenzyl idenesorbitol (hemiacetal) formed from benzaldehyde and its derivatives with sorbitol, and tribenzyl idenesorbitol (triacetal) formed from benzaldehyde and its derivatives with sorbitol. Benzaldehyde and its derivatives are specifically described above and will not be described here again.
The content of the by-product in the waste residue may be 15 to 35wt%. In certain embodiments, the by-product is present in the waste residue in an amount of 20 to 30wt%.
The target product is dibenzylidene sorbitol formed by formaldehyde and derivatives thereof and sorbitol. Benzaldehyde and its derivatives are specifically described above and will not be described here again.
The content of the target product in the waste residue can be 50-70 wt%. In certain embodiments, the target product is present in the waste residue in an amount of 55 to 65wt%.
The salt produced by acid-base neutralization may be present in the waste residue in an amount of 5 to 15wt%. In certain embodiments, the salt resulting from acid-base neutralization is present in the waste residue in an amount of 8 to 12wt%.
In the initial reaction system, the monohydric alcohol is 150-650 parts by volume; preferably 200 to 600 parts by volume. In some embodiments, the monohydric alcohol may be 300 to 400 parts by volume.
The monohydric alcohol may be an aliphatic monohydric alcohol having 1 to 6 carbon atoms. Preferably, the monohydric alcohol is an aliphatic monohydric alcohol having 1 to 3 carbon atoms. The aliphatic monohydric alcohol may be a linear monohydric alcohol or a branched monohydric alcohol. Examples of monohydric alcohols include, but are not limited to, methanol, ethanol.
In the initial reaction system, 700-1300 parts by volume of water; preferably 800 to 1200 parts by volume. In certain embodiments, the water is present in an amount of 900 to 1000 parts by volume.
In the initial reaction system, the volume ratio of water to monohydric alcohol may be (1-7): 1. In certain embodiments, the volume ratio of water to monohydric alcohol is (2-5): 1. In other embodiments, the volume ratio of water to monohydric alcohol is (3-4): 1.
In the initial reaction system, the mass volume ratio of the waste residue to the monohydric alcohol is (250-800): 150-650 kg/L; preferably (300-750) kg/L (200-600). In certain embodiments, the mass to volume ratio of the waste residue to the monohydric alcohol is 1 (0.2 to 2.5) kg/L. In other embodiments, the mass to volume ratio of the waste residue to the monohydric alcohol is 1 (0.5-2) kg/L. In still other embodiments, the mass to volume ratio of the waste residue to the monohydric alcohol is 1 (1 to 1.5) kg/L.
The acidic compound is selected from one or more of sulfuric acid, hydrochloric acid, benzenesulfonic acid shown in formula (II) and derivatives thereof.
In the formula (II), R 3 And R is 4 Independently selected from H, C to C6 alkyl groups. Preferably, R 3 And R is 4 Independently selected from H, C to C3 alkyl groups.
In certain embodiments, R 3 H. R is R 4 Selected from H, C to C3 alkyl groups. Preferably, R 4 Selected from H and methyl. R is R 4 May be located in the ortho, meta or para position to the sulfonic acid group.
Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, methylpropyl, pentyl, methylbutyl, dimethylpropyl, ethylpropyl, hexyl, methylpentyl, dimethylbutyl, ethylbutyl.
Examples of benzenesulfonic acid and its derivatives include, but are not limited to, benzenesulfonic acid, p-toluenesulfonic acid.
The mass ratio of the waste residue to the acid compound is (250-800): (1-10). Preferably, the mass ratio of the waste residue to the acid compound is (300-750): (2-8). In certain embodiments, the mass ratio of waste residue to acidic compound is 1: (0.002:0.02). In other embodiments, the mass ratio of waste residue to acidic compound is 1: (0.004:0.015).
The above materials can be controlled within the above dosage range, so that acetal and hemiacetal materials in waste residue can be fully hydrolyzed, and the recovery rate of aromatic aldehyde materials can be improved.
The reaction temperature of the initial reaction system is 60-95 ℃; preferably, the reaction temperature is 70 to 90 ℃. In certain embodiments, the reaction temperature is 75 to 85 ℃.
In certain embodiments, the waste residue, the monohydric alcohol, and the acidic material are mixed to obtain a mixture; water was added to the mixture at the reaction temperature to form an initial reaction system.
The initial reaction system reacts for 0.5 to 3 hours; preferably 1 to 2 hours; more preferably 1 to 1.5 hours, water is added to the reaction system to continue the reaction. After the initial reaction system reacts for a period of time, the water in the reaction system is reduced, so that the hydrolysis of acetal and hemiacetal is not facilitated, and the recovery rate of aromatic aldehyde substances can be further improved by adding a proper amount of water into the reaction system.
Adding 300-500 parts by volume of water into the reaction system; preferably 350 to 450 parts by volume; more preferably 400 to 450 parts by volume.
After water is added into the reaction system, the temperature can be 60-95 ℃; preferably 70-90 ℃; more preferably 75 to 85 ℃.
The reaction is continued for 0.5-3 h; preferably 1 to 2 hours; more preferably 1 to 1.5 hours.
In certain embodiments, water is added to the reaction system at a flow rate of 100 to 300L/h. Preferably, water is added to the reaction system at a flow rate of 150 to 250L/h.
The above reaction can be carried out in an enamel reactor.
In some embodiments, the method may further comprise the steps of: and (3) standing and layering a reaction product obtained by continuing the reaction after adding water, rectifying and purifying an upper oil phase to obtain benzaldehyde and derivatives thereof. The rectification and purification are carried out by a method conventional in the art, and are not described herein.
The raw materials used in the following examples are described below:
the waste residue is obtained by the following method: and (3) carrying out condensation reaction on sorbitol and aromatic aldehyde substances corresponding to the product in the presence of an acid catalyst and a solvent to obtain a reaction product. And (3) carrying out filter pressing and washing on the reaction product in a filter press to obtain a solid crude product and a solvent system. Distilling the solvent system to obtain waste residue.
Example 1
Waste residue collected in the production process of 508kg of 1,3:2, 4-di (3, 4-dimethylbenzylidene) sorbitol is placed in a 3000L enamel reactor, and then 200L of methanol and 5kg of p-toluenesulfonic acid are sequentially added into the enamel reactor. Closing the feeding hole, starting stirring and steam heating, heating the enamel reaction kettle to 70 ℃, and then adding 1000L of water into the enamel reaction kettle to carry out hydrolysis reaction on substances in the enamel reaction kettle. After 1h of reaction, water was then added again to the reaction vessel at a water flow rate of 200L/h for a duration of 2h, and then reacted at 70℃for 1h to give a reaction product.
And standing and layering the reaction product, discharging a lower water phase, collecting an upper oil phase, and rectifying and purifying to obtain 152kg of liquid product. The liquid product obtained by gas chromatography detection is 3, 4-dimethylbenzaldehyde with the purity of 98.24 percent.
Example 2
470kg of waste residue collected in the production process of 1,3:2, 4-dibenzylidene sorbitol is placed in a 3000L enamel reactor, and then 200L of methanol and 2kg of sulfuric acid are sequentially added into the enamel reactor. Closing the feeding hole, starting stirring and steam heating, heating the enamel reaction kettle to 75 ℃, and then adding 850L of water into the enamel reaction kettle to carry out hydrolysis reaction on substances in the enamel reaction kettle. After 1h of reaction, water was again added to the reaction vessel at a flow rate of 200L/h for a duration of 2h, and then reacted at 75℃for 1h to give a reaction product.
And standing and layering the reaction product, discharging a lower water phase, collecting an upper oil phase, and rectifying and purifying to obtain 118.4kg of liquid product. The liquid product was benzaldehyde with a purity of 97.65% as measured by gas chromatography.
Example 3
315kg of waste residue collected in the production process of 1,3:2, 4-dibenzylidene sorbitol is placed in a 3000L enamel reactor, and 600L of methanol and 4.5kg of sulfuric acid are sequentially added into the enamel reactor. Closing the feeding hole, starting stirring and steam heating, heating the enamel reaction kettle to 85 ℃, and then adding 850L of water into the enamel reaction kettle to carry out hydrolysis reaction on substances in the enamel reaction kettle. After 1h of reaction, water was again added to the reaction vessel at a flow rate of 200L/h for a duration of 2h, and then reacted at 85℃for 1h to give a reaction product.
And standing and layering the reaction product, discharging a lower water phase, collecting an upper oil phase, and rectifying and purifying to obtain 78.6kg of liquid product. The liquid product was benzaldehyde with a purity of 98.97% as measured by gas chromatography.
Example 4
600kg of waste residue collected in the production process of 1,3:2, 4-di (p-methylbenzylidene) sorbitol is placed in a 3000L enamel reactor, and then 500L of methanol and 7kg of p-toluenesulfonic acid are sequentially added into the enamel reactor. Closing the feeding hole, starting stirring and steam heating, heating the enamel reaction kettle to 80 ℃, and then adding 1200L of water into the enamel reaction kettle to carry out hydrolysis reaction on substances in the enamel reaction kettle. After 1h of reaction, water was again added to the reaction vessel at a flow rate of 200L/h for a duration of 2h, and then reacted at 80℃for 1h to give a reaction product.
And standing and layering the reaction product, discharging a lower water phase, collecting an upper oil phase, and rectifying and purifying to obtain 166.9kg of liquid product. The liquid product obtained by gas chromatography detection is p-tolualdehyde with the purity of 96.74 percent.
Example 5
Waste residues collected in the production process of 712kg of 1,3:2, 4-di (3, 4-dimethylbenzylidene) sorbitol are placed in a 3000L enamel reactor, and then 500L of methanol and 8kg of p-toluenesulfonic acid are sequentially added into the enamel reactor. Closing the feeding hole, starting stirring and steam heating, heating the enamel reaction kettle to 90 ℃, and then adding 1200L of water into the enamel reaction kettle to carry out hydrolysis reaction on substances in the enamel reaction kettle. After 1h of reaction, water was again added to the reaction vessel at a flow rate of 200L/h for a duration of 2h, and then reacted at 90℃for 1h to give a reaction product.
And standing and layering the reaction product, discharging a lower water phase, collecting an upper oil phase, and rectifying and purifying to obtain 222.5kg of liquid product. The liquid product obtained by gas chromatography detection is 3, 4-dimethylbenzaldehyde with the purity of 98.66 percent.
The present invention is not limited to the above-described embodiments, and any modifications, improvements, substitutions, and the like, which may occur to those skilled in the art, fall within the scope of the present invention without departing from the spirit of the invention.
Claims (10)
1. A method for treating waste residues is characterized in that the waste residues are obtained in the production process of dibenzylidene sorbitol;
the method comprises the following steps: reacting an initial reaction system containing waste residues, 150-650 parts by volume of monohydric alcohol, acid compounds and 700-1300 parts by volume of water for 0.5-3 hours, then adding 300-500 parts by volume of water into the reaction system, and continuing the reaction;
wherein the mass volume ratio of the waste residue to the monohydric alcohol is (250-800): 150-650 kg/L.
2. The method according to claim 1, wherein the waste residue contains sorbitol, benzaldehyde and its derivatives represented by formula (I), monobenzyl sorbitol formed by benzaldehyde and its derivatives represented by formula (I) and sorbitol, dibenzylidene sorbitol formed by benzaldehyde and its derivatives represented by formula (I) and sorbitol, and tribenzyl sorbitol formed by benzaldehyde and its derivatives represented by formula (I) and sorbitol;
in the formula (I), R 1 And R is 2 Independently selected from H, C to C6 alkyl groups.
3. The method according to claim 2, wherein the benzaldehyde and its derivative are one or more selected from the group consisting of 3, 4-dimethylbenzaldehyde, benzaldehyde and p-methylbenzaldehyde.
4. The method according to claim 1, wherein the mass ratio of the waste residue to the acidic compound is (250 to 800): (1-10).
5. The process according to claim 1, wherein the monohydric alcohol is an aliphatic monohydric alcohol having 1 to 6 carbon atoms, and the acidic compound is selected from sulfuric acid, hydrochloric acid, benzenesulfonic acid represented by formula (II) and derivatives thereof;
in the formula (II), R 3 And R is 4 Independently selected from H, C to C6 alkyl groups.
6. The process according to claim 5, wherein the monohydric alcohol is an aliphatic monohydric alcohol having 1 to 3 carbon atoms, R 3 And R is 4 Independently selected from H, C to C3 alkyl groups.
7. The method according to claim 1, wherein the initial reaction system is reacted at 60 to 95℃and the reaction is continued at 60 to 95℃for 0.5 to 3 hours after the addition of water.
8. The process according to claim 1, wherein water is added to the reaction system at a flow rate of 100 to 300L/h.
9. The method according to claim 1, wherein the waste residue, the monohydric alcohol and the acidic compound are mixed to obtain a mixture; water was added to the mixture at the reaction temperature to form an initial reaction system.
10. The method according to any one of claims 1 to 9, characterized by further comprising the steps of:
and (3) standing and layering a reaction product obtained by continuing the reaction after adding water, rectifying and purifying the oil phase to obtain benzaldehyde and derivatives thereof.
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| CN202311721540.4A CN117720407A (en) | 2023-12-14 | 2023-12-14 | Waste residue treatment method |
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| CN202311721540.4A CN117720407A (en) | 2023-12-14 | 2023-12-14 | Waste residue treatment method |
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