CN116440521A - Method and system for efficiently improving quality of benzaldehyde by oxidation method and application of method and system - Google Patents
Method and system for efficiently improving quality of benzaldehyde by oxidation method and application of method and system Download PDFInfo
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- CN116440521A CN116440521A CN202310285781.2A CN202310285781A CN116440521A CN 116440521 A CN116440521 A CN 116440521A CN 202310285781 A CN202310285781 A CN 202310285781A CN 116440521 A CN116440521 A CN 116440521A
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- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 title claims abstract description 390
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 title claims abstract description 195
- 238000000034 method Methods 0.000 title claims abstract description 76
- 230000003647 oxidation Effects 0.000 title claims abstract description 45
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 45
- 238000012856 packing Methods 0.000 claims abstract description 74
- 239000000945 filler Substances 0.000 claims abstract description 67
- 229910052751 metal Inorganic materials 0.000 claims abstract description 63
- 239000002184 metal Substances 0.000 claims abstract description 63
- 239000000872 buffer Substances 0.000 claims abstract description 53
- 239000002131 composite material Substances 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 32
- 238000004821 distillation Methods 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 24
- 150000002978 peroxides Chemical class 0.000 claims abstract description 13
- 150000007524 organic acids Chemical class 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 68
- 239000005711 Benzoic acid Substances 0.000 claims description 34
- 235000010233 benzoic acid Nutrition 0.000 claims description 34
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000005070 sampling Methods 0.000 claims description 10
- 230000009471 action Effects 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 239000000047 product Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 13
- 239000012043 crude product Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 239000000543 intermediate Substances 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000006872 improvement Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 229960002903 benzyl benzoate Drugs 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
- B01D3/146—Multiple effect distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/14—Production of inert gas mixtures; Use of inert gases in general
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/30—Loose or shaped packing elements, e.g. Raschig rings or Berl saddles, for pouring into the apparatus for mass or heat transfer
-
- 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
-
- 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
- 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
- C07C45/85—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method, a system and application thereof for efficiently improving the quality of benzaldehyde by an oxidation method, wherein the system comprises a packed tower, a buffer chamber at the top of the packed tower, a middle tank communicated with the buffer chamber through a first pipeline and a power assembly; the bottom of the packing tower is provided with a material inlet for inputting benzaldehyde, a packing layer is arranged in the packing tower, and the packing layer is composite active metal packing. The system is arranged between a primary distillation tower and a rectifying tower of the benzaldehyde production device by an oxidation method, benzaldehyde output by the primary distillation tower is continuously transferred into a filler tower, and is continuously transferred to the rectifying tower from a middle tank after being acted by a composite metal filler layer. The method utilizes the active metal filler to remove trace peroxide and organic acid in the benzaldehyde, improves the quality stability of the rectified benzaldehyde, reduces the acid value and achieves the optimal quality; and through the continuous operation of the system, the rectified benzaldehyde product has low acid value, low color number and high content, meets the food-grade requirement, has stable quality and can be stored for a long time.
Description
Technical Field
The invention relates to the technical field of benzaldehyde preparation, in particular to a method and a system for efficiently improving the quality of oxidized benzaldehyde and application thereof.
Background
The oxidation benzaldehyde is obtained by catalytic oxidation of toluene. During oxidation, a range of intermediates of varying degrees of oxidation, such as benzyl alcohol, benzaldehyde, benzoic acid, benzyl benzoate, etc., are formed; then, crude products of benzaldehyde, benzyl alcohol, benzoic acid, benzyl benzoate and the like with different boiling points are obtained through repeated rectification and separation, and commercial-grade benzaldehyde, benzoic acid and benzyl benzoate with high content and high quality are obtained through further purification. Because the benzaldehyde raw material prepared by the oxidation method has no chlorine in the whole reaction process, compared with benzaldehyde prepared by the chlorination method, the obtained commercial grade benzaldehyde has no chlorine, and is popular in the fields of cosmetics and fine chemicals.
The crude product of the benzaldehyde zone is mainly benzaldehyde, in which small amounts of benzoic acid are entrapped. The traditional process for removing benzoic acid in benzaldehyde comprises the steps of firstly washing a crude benzaldehyde product with alkali to remove acid, dehydrating, and then rectifying to obtain industrial-grade benzoic acid or further purifying to obtain food-grade benzaldehyde. For example, the invention patent (application number is CN 202110754770.5) discloses a method for recovering food-grade benzaldehyde from benzoic acid rectifying low-boiling-point substances, namely, washing by adopting aqueous solution such as sodium carbonate or sodium bicarbonate, removing acid and ester organic matters in the benzaldehyde, washing by using purified water, and removing alkali dissolved in the benzaldehyde to obtain the food-grade benzaldehyde. However, a large amount of organic alkaline wastewater generated after alkaline washing and water washing becomes a difficult problem of environmental protection treatment, and benzoic acid removed by alkaline washing cannot be effectively recycled, and huge resource waste is caused.
At present, the refining process of crude benzaldehyde can be realized by replacing the traditional alkali washing water washing method with a finely controlled rectification acid removal scheme, and the industrial grade benzaldehyde is obtained. However, in practical application, the problem that the acid value and the color number are increased after long-term storage appears in the process of preserving the benzaldehyde prepared by an oxidation method and a rectification acid removal method, and the problem has become a difficult problem faced by the oxidation method benzaldehyde at present. Through analysis and identification of the quality change of benzaldehyde by an oxidation method, the color stability and content of finished benzaldehyde can be influenced by the generated intermediate peroxybenzoic acid in the process of oxidizing toluene to generate benzoic acid. Since the boiling point of peroxybenzoic acid is close to that of benzaldehyde, the physical and chemical properties and structure are similar to those of benzaldehyde, so that the peroxybenzoic acid cannot be completely removed in rectification; as a small amount of peroxybenzoic acid is still entrained in the rectified benzaldehyde finished product, active groups are gradually decomposed in the placing process, and various side reactions are generated with the benzaldehyde, so that the acid value of the finished benzaldehyde is increased from 0.1 to 0.15-0.25, the content is reduced from 99.9% to 99.7-99.88%, the color number is slowly increased from No. 10 to 30-50, and the maximum can be more than 100. The method for removing the acid by rectification can not remove the peroxybenzoic acid in the benzaldehyde by an oxidation method, so that the current benzaldehyde by oxidation and rectification can not meet the requirements of high-quality benzaldehyde or food-grade benzaldehyde; while the traditional method of alkali washing and water washing can effectively remove the peroxybenzoic acid and other organic acids, the double pressure based on environmental protection and economy makes it impossible to compromise the old way of reusing the alkali washing and water washing to generate a large amount of waste water containing saline and alkaline.
In view of the above, there is a need to design an improved environment-friendly method, system and application thereof for improving the quality of oxidized benzaldehyde.
Disclosure of Invention
The invention aims to provide a method and a system for efficiently improving the quality of benzaldehyde by an oxidation method and application thereof, wherein the system is applied between a primary distillation tower and a rectifying tower of a benzaldehyde production device by the oxidation method, a crude product benzaldehyde obtained by the primary distillation tower is treated by adopting a composite active metal filler in a filler tower of the system, peroxybenzoic acid and other organic acids in the crude product benzaldehyde are removed, and the quality of the benzaldehyde is improved by the cooperative cooperation of devices in the system, so that the benzaldehyde which enters the rectifying tower for deep purification has the advantages of low acid value, low color number, high content, no peculiar smell, meeting the requirements of food-grade benzaldehyde, along with stable quality and long preservation time.
In order to achieve the aim, the invention provides a system for efficiently improving the quality of benzaldehyde by an oxidation method, which comprises a packed tower, a buffer chamber at the top of the packed tower, a middle tank communicated with the buffer chamber through a first pipeline and a power assembly, wherein the packed tower is communicated with the buffer chamber; the bottom of the packing tower is provided with a material inlet for inputting benzaldehyde, a packing layer is arranged in the packing tower, and the packing layer comprises composite active metal packing;
the benzaldehyde is powered by the power component, enters the packing tower from the material inlet, passes through the action of the packing layer, reaches the buffer chamber, enters the intermediate tank through the first pipeline, and is finally output by the intermediate tank.
As a further improvement of the invention, the composite active metal filler in the filler layer comprises one or more of Zn, mg, al, ca, fe, cu and Sn with different particle sizes.
As a further improvement of the invention, the particle size of the composite active metal filler is 1 mm-5 mm so as to ensure that sufficient gaps exist between the fillers to allow benzaldehyde materials to pass through.
As a further improvement of the invention, the buffer chamber contains nitrogen, and the buffer chamber is provided with a nitrogen replacement device for replacing and removing trace hydrogen generated after the benzoic acid, the peroxybenzoic acid and the composite active metal filler in the benzaldehyde react.
As a further improvement of the invention, the first pipeline is provided with an upward bent U-shaped bent pipe, and the U-shaped bent pipe is arranged at a position close to the joint of the first pipeline and the buffer chamber; the upward bent U-shaped bend is arranged to prevent the generated trace hydrogen from entering the intermediate tank.
As a further improvement of the invention, the tower body of the packed tower is provided with the packing holes, and the packing holes are manholes, so that the composite active metal packing in the packed tower is replaced conveniently.
As a further improvement of the invention, the first pipeline is provided with a sampling port so as to detect the content of peroxide and acid in the sample in real time.
The application of the system for efficiently improving the quality of the benzaldehyde by an oxidation method is characterized in that the system for efficiently improving the quality of the benzaldehyde by the oxidation method is arranged between a primary distillation tower and a rectifying tower of a benzaldehyde production device by the oxidation method in practical application, benzaldehyde output from the primary distillation tower is continuously transferred into a material inlet at the bottom of a packing tower, is output from a middle tank after being processed by the system, and enters the rectifying tower for continuous rectification and purification, so that the continuous operation of the system for efficiently improving the quality of the benzaldehyde by the oxidation method is realized.
The invention also provides a method for efficiently improving the quality of the oxidized benzaldehyde, which adopts a system for efficiently improving the quality of the oxidized benzaldehyde to treat the benzaldehyde output by the primary distillation tower so as to remove the peroxide and the residual organic acid in the benzaldehyde;
the method comprises the steps of continuously inputting benzaldehyde output from a primary distillation tower into a packing tower, providing power by a power component, enabling the benzaldehyde to enter from a material inlet at the bottom of the packing tower, removing peroxide and other organic acids from the benzaldehyde under the action of composite active metal packing in a packing layer, enabling the benzaldehyde to reach a buffer chamber, enabling the benzaldehyde to enter a middle tank through a first pipeline, outputting the benzaldehyde from the middle tank, continuously transferring the benzaldehyde into a rectifying tower, and further rectifying and purifying the benzaldehyde to obtain high-purity benzaldehyde.
As a further improvement of the invention, the residence time of the benzaldehyde in the filler layer is 2-4 h; the buffer chamber adopts a nitrogen replacement device, and nitrogen replacement is carried out on the buffer chamber every 1-3 h.
The beneficial effects of the invention are as follows:
1. the invention provides a method, a system and application thereof for efficiently improving the quality of benzaldehyde by an oxidation method, wherein the system comprises a packing tower, a buffer chamber at the top of the packing tower, a middle tank and a power assembly, wherein the middle tank is communicated with the buffer chamber through a first pipeline, and the packing tower is communicated with the buffer chamber; the bottom of the packing tower is provided with a material inlet for inputting benzaldehyde, a packing layer is arranged in the packing tower, and the packing layer is composite active metal packing. In practical application, the system is arranged between a primary distillation tower and a rectifying tower of an oxidation method benzaldehyde production device, a benzaldehyde crude product output from the primary distillation tower is input into a packing tower, power is provided by a power component, and the benzaldehyde crude product enters the packing tower from a material inlet at the bottom; and removing trace amounts of peroxybenzoic acid and benzoic acid from the mixture by the action of the packing layer, enabling the mixture to reach the buffer chamber, enabling the mixture to enter the intermediate tank through the first pipeline, enabling the mixture to be output from the intermediate tank, and enabling the mixture to enter the rectifying tower for further rectification and purification. The invention removes trace peroxybenzoic acid and benzoic acid in benzaldehyde by using the composite active metal filler in the system filler tower, and improves the quality of benzaldehyde by the cooperative cooperation of devices in the system, so that the rectified benzaldehyde has low acid value, low color number, high content, no peculiar smell, and stable quality, and meets the requirements of food-grade benzaldehyde.
2. According to the invention, the composite active metal filler is arranged in the filler tower, and after the active metal is contacted with the benzaldehyde crude product output by the primary distillation tower, the acid-base reaction and the oxidation-reduction reaction are carried out on the surface of the active metal and the peroxybenzoic acid and the benzoic acid, so that the peroxybenzoic acid and the benzoic acid are removed, the quality stability of the rectified benzaldehyde product is improved, and the rectified benzaldehyde product can be stored for a long time without deterioration. The composite active metal filler also utilizes the synergistic effect of multiple metals, so that the oxidation-reduction function of the composite metal and the peroxide and the acid-base neutralization function of the composite metal and the trace benzoic acid are fully exerted and are effective for a long time, and the deactivation of the composite metal, such as calcium, aluminum, iron and the like, after the composite metal reacts with the peroxide to generate metal oxides, is prevented. In addition, the composite active metal filler removes trace benzoic acid carried in benzaldehyde, so that the reflux ratio of a rectifying tower can be reduced, the rectifying efficiency is improved, the energy consumption and the residence time are reduced, and finally, the product with high quality and meeting the requirements of food-grade benzaldehyde is prepared.
3. According to the invention, a power device is utilized to continuously input a benzaldehyde crude product output by a primary distillation tower from the bottom of a filler tower, materials enter a composite active metal filler from bottom to top, and the anti-gravity arrangement enables acidic and oxidative materials in benzaldehyde to fully contact and react with the composite active metal filler, so that trace peroxybenzoic acid and benzoic acid in the benzaldehyde are efficiently removed; meanwhile, by controlling the residence time of the benzaldehyde in the composite active metal filler, a small amount of peroxybenzoic acid and benzoic acid in the benzaldehyde are ensured to be reacted by the active metal; and a positive U-shaped bent pipe is arranged on the first pipeline close to the buffer chamber, so that hydrogen is prevented from escaping, and the safety of the system is ensured.
Drawings
FIG. 1 is a schematic diagram of the system composition and workflow for improving the quality of oxidized benzaldehyde.
Reference numerals
100-a system for improving the quality of benzaldehyde by an oxidation method with high efficiency; 110-packed column; 111-material inlet; 112-a filler layer; 113-a filler hole; 114-sieve plate; 120-buffer chamber; 121-nitrogen displacement device; 130-an intermediate tank; 140-a first pipe; 141-U-shaped bent pipe; 142-sampling port.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Referring to fig. 1, a system 100 for efficiently improving the quality of benzaldehyde by oxidation method includes a packed tower 110, a buffer chamber 120 at the top of the packed tower 110, a middle tank 130 communicating with the buffer chamber 120 through a first pipeline 140, and a power assembly, wherein the packed tower 110 is communicated with the buffer chamber 120; the bottom of the packing tower 110 is provided with a material inlet 111 for inputting benzaldehyde, a packing layer 112 is arranged in the packing tower 110, and the packing layer 112 comprises composite active metal packing; the benzaldehyde is powered by the power component, enters the packed tower 110 from the material inlet 111, passes through the action of the packing layer 112, reaches the buffer chamber 120, enters the intermediate tank 130 through the first pipeline 140, and is finally output from the intermediate tank 130. The invention removes trace peroxide and organic acid in the benzaldehyde by utilizing the composite active metal filler in the system filler tower 110, and improves the quality of the benzaldehyde by the cooperative cooperation of devices in the system, so that the rectified benzaldehyde has low acid value, low color number, high content, no peculiar smell, and stable quality, and meets the requirements of food-grade benzaldehyde.
Specifically, the composite active metal filler in filler layer 112 includes one or more of Zn, mg, al, ca, fe, cu, sn of different particle sizes. The particle size of the composite active metal filler is 1 mm-5 mm, so that sufficient gaps are ensured between the fillers to enable benzaldehyde materials to pass through. Because the peroxybenzoic acid is generated in the process of oxidizing the methylbenzene into the benzoic acid by the oxidation method, the boiling point of the peroxybenzoic acid is close to that of the benzaldehyde, the structure is similar, and the content of the peroxybenzoic acid is low, so that the peroxybenzoic acid cannot be completely removed in the rectification of the benzaldehyde, and the stability of a benzaldehyde product is affected. The invention sets composite active metal filler in the filler tower, and the crude benzaldehyde product output from the primary distillation tower contacts with the filler to generate metal oxide or react with the filler to generate metal salt, so the acid value of the benzaldehyde product refined by the rectifying tower is lower, no peroxide exists, and the quality can be kept stable and the benzaldehyde product is not deteriorated after long-term storage. The composite active metal filler also utilizes the synergistic effect of multiple metals, so that the oxidation-reduction function of the composite metal and the peroxide and the acid-base neutralization function of the composite metal and the trace organic acid are fully exerted and are effective for a long time, and the deactivation of metal oxides generated by the reaction of some metals such as calcium, aluminum, iron and the like with the peroxide is prevented. In addition, the composite metal of the active metal filler can remove part of benzoic acid in the benzaldehyde, so that the separation pressure of a benzaldehyde rectifying tower working section is reduced, the rectifying efficiency is improved, the energy consumption is reduced, the residence time is reduced, and finally, the product with low acid value and high quality meeting the requirements of food-grade benzaldehyde is prepared.
In some specific embodiments, the active metal filler may be periodically regenerated with low concentration acid water to remove metal salts and oxide passivation layers therefrom, and the regenerated active metal filler may be further used in the filler column 110 after water removal to reduce the preparation cost of refining benzaldehyde.
Specifically, the buffer chamber 120 contains nitrogen, and the buffer chamber 120 is provided with a nitrogen replacement device 121 to replace and remove trace hydrogen generated after the benzoic acid and the peroxybenzoic acid in the benzaldehyde react with the composite active metal filler. The first pipe 140 is provided with a U-shaped bent pipe 141 which is bent upwards, and the U-shaped bent pipe 141 is arranged at a position close to the joint of the first pipe 140 and the buffer chamber 120; the U-shaped bent pipe 141 can prevent hydrogen from entering the rectifying tower, and ensures the safety of the system.
The invention uses the power device to continuously input the benzaldehyde crude product output by the primary distillation tower from the bottom of the packing tower 110, the material enters the composite active metal packing from bottom to top, and the anti-gravity arrangement ensures that the benzaldehyde material fully contacts with the composite active metal packing, so that trace peroxybenzoic acid and benzoic acid in the benzaldehyde are better removed.
In some specific embodiments, the tower body of the packed tower 110 is provided with a packing hole 113, and the packing hole 113 is provided with a manhole, so that the composite active metal packing in the packed tower 110 is replaced conveniently. The upper and lower interfaces of the packing layer 111 inside the packing tower 110 are provided with screen plates 114, so that the benzoic acid material can pass through from bottom to top, and the packing is not carried out.
In some embodiments, the first pipe 140 is provided with a sampling port 142, so as to detect the content of peroxybenzoic acid in the sample in real time.
In some specific embodiments, valves are arranged between the material inlet 111 at the bottom of the packed tower 110 and the primary distillation tower, and between the middle tank 130 and the rectifying tower. And the outlet of the nitrogen replacement device 121 is also provided with a valve, so that the tightness during the operation of the system is realized.
The application of the system 100 for efficiently improving the quality of the benzaldehyde by an oxidation method is that the system 100 is arranged between a primary distillation tower and a rectifying tower of a benzaldehyde production device by the oxidation method in practical application, benzaldehyde output from the primary distillation tower is continuously input into a material inlet 111 at the bottom of a packing tower 110, is output from a middle tank 130 after being processed by the system, and enters the rectifying tower for continuous rectification and purification, so that the continuous operation of the system for efficiently improving the quality of the benzaldehyde by the oxidation method is realized.
A method for efficiently improving the quality of benzaldehyde by an oxidation method comprises the steps of adopting a system for efficiently improving the quality of benzaldehyde by an oxidation method to treat benzaldehyde output by a primary distillation tower so as to remove peroxybenzoic acid and benzoic acid in the benzaldehyde; specifically, the benzaldehyde output from the primary distillation tower is input into a filler tower 110, and is powered by a power component, so that the benzaldehyde enters from a material inlet 111 at the bottom of the filler tower 110, the peroxybenzoic acid and the benzoic acid in the benzaldehyde are removed under the action of composite active metal filler in a filler layer 112, the benzaldehyde reaches a buffer chamber 120, then enters a middle tank 130 through a first pipeline 140, finally the benzaldehyde is output from the middle tank 130, and continuously enters a rectifying tower for further rectification and purification to obtain high-purity benzaldehyde.
Specifically, the residence time of benzaldehyde in the filler layer 112 is 2 to 4 hours; by controlling the residence time of the benzaldehyde in the composite active metal filler, the reaction of a small amount of peroxyformic acid and benzoic acid in the benzaldehyde by the active metal is ensured to be complete.
In some embodiments, the buffer chamber 120 employs a nitrogen gas displacement device 121 to displace nitrogen gas from the buffer chamber 120 every 1-3 hours.
Example 1
The embodiment provides a method, a system and an application thereof for efficiently improving the quality of benzaldehyde by an oxidation method, wherein the system is shown in fig. 1, and comprises a packed tower 110, a buffer chamber 120 at the top of the packed tower 110, a middle tank 130 communicated with the buffer chamber 120 through a first pipeline 140 and a power assembly, and the packed tower 110 is communicated with the buffer chamber 120; the bottom of the packed tower 110 is provided with a material inlet 111 for inputting benzaldehyde, a packed layer 112 is arranged in the packed tower 110, and the upper and lower interfaces of the packed layer 111 are provided with a sieve plate 114; the filler layer 112 is a composite active metal filler, the composite active metal filler is Zn and Mg, and the particle size is 3-5 mm. The buffer chamber 120 is provided with a nitrogen gas displacement device 121; the first pipe 140 is provided with a U-shaped bent pipe 141 which is bent upwards, and the U-shaped bent pipe 141 is arranged at a position close to the joint of the first pipe 140 and the buffer chamber 120; the tower body of the packed tower 110 is provided with a packed hole 113, and the first pipeline 140 is provided with a sampling port 142.
The working principle of the system is as follows:
the system 100 is arranged between a primary distillation tower and a rectifying tower of an oxidation method benzaldehyde production device, benzaldehyde output from the primary distillation tower is input into a filler tower 110, power is provided by a power component, the benzaldehyde continuously enters from a material inlet 111 at the bottom of the filler tower 110, trace amounts of peroxybenzoic acid and benzoic acid are removed through the action of composite active metal filler in a filler layer 112, the peroxybenzoic acid and the benzoic acid reach a buffer chamber 120, the buffer chamber enters a middle tank 130 through a first pipeline 140, and finally the benzaldehyde is output from the middle tank 130 and continuously enters the rectifying tower for further rectification and purification. Wherein the residence time of benzaldehyde in filler layer 112 is 3h; the buffer chamber 120 is replaced with nitrogen gas by using a nitrogen gas replacement device 121 every 2 hours.
Sampling and detecting materials from a sampling port 142; and the rectified product treated by the system of the embodiment 1 and then treated by the rectifying tower is stored for 90 days, and then sampling detection is carried out. The test items including acid value, color number and benzaldehyde content gave the results shown in Table 1.
Comparative example 1
Comparative example 1 provides a treatment method of benzaldehyde by oxidation, wherein the system 100 for efficiently improving the quality of benzaldehyde by oxidation as in example 1 is not arranged between a primary distillation tower and a rectifying tower, and the benzaldehyde crude product of the primary distillation tower in comparative example 1 directly enters the rectifying tower for rectifying treatment.
Sampling and detecting the benzaldehyde material prepared by rectifying the comparative example 1; and after 90 days of storage, sampling and detection are carried out. The test items including acid value, color number and benzaldehyde content gave the results shown in Table 1.
Table 1 results of product measurements for example 1 and comparative example 1
As is clear from Table 1, in example 1, after systematic treatment between the primary distillation and the rectification, a benzaldehyde product having a low acid value, a low color number and a high content, satisfying the requirements of food-grade benzaldehyde, was obtained. After the product is stored for 90 days, the acid value and the color number of the product are more stable than those of the product of comparative example 1. This shows that the benzaldehyde product prepared in example 1 has good quality, long-term storage without deterioration and stable quality.
Comparative example 2
The comparative example 2 provides a method, a system and an application thereof for improving the quality of benzaldehyde by an oxidation method, which are different from those of the example 1 in that the particle size of the composite active metal filler is 8-10 mm, and the rest is approximately the same as that of the example 1, and no description is repeated here.
Comparative example 3 provides a method, system and application thereof for improving the quality of benzaldehyde by oxidation method, which are different from example 1 in that the retention time of benzaldehyde in the filler layer 112 is 1h, and the rest is substantially the same as example 1, and will not be described herein.
The results of the detection of the acid value, color number and benzaldehyde content of the rectified products of comparative example 2 and comparative example 3 and the products after 90 days of holding are shown in Table 2.
Table 2 results of the measurements of the products of comparative examples 1 to 2
As can be seen from table 2, the detection results of example 1 and comparative examples 2 to 3 show that the particle size of the composite active metal filler is large, so that the reaction between the benzaldehyde material and the composite active metal filler in the filler layer is insufficient, and the removal effect of peroxybenzoic acid is slightly low; and the retention time of benzaldehyde in the filler layer is too short, so that the removal effect of the peroxybenzoic acid is poor, the quality stability of the rectified product is poor, and the acid value and the color number are both increased after 90 days.
In summary, the invention provides a method, a system and application thereof for efficiently improving the quality of benzaldehyde by an oxidation method, wherein the system comprises a packed tower, a buffer chamber at the top of the packed tower, a middle tank and a power assembly, wherein the middle tank is communicated with the buffer chamber through a first pipeline, and the packed tower is communicated with the buffer chamber; the bottom of the packing tower is provided with a material inlet for inputting benzaldehyde, a packing layer is arranged in the packing tower, and the packing layer is composite active metal packing. In practical application, the system is arranged between a primary distillation tower and a rectifying tower of the device for producing benzaldehyde by an oxidation method, a benzaldehyde crude product output from the primary distillation tower is continuously input into a packing tower, power is provided by a power component, and the benzaldehyde crude product enters the packing tower from a material inlet at the bottom; and through the action of the packing layer, the peroxybenzoic acid and the benzoic acid in the buffer chamber are removed, the buffer chamber is filled with the peroxybenzoic acid and the benzoic acid, the buffer chamber enters the intermediate tank through the first pipeline, and finally the buffer tank outputs the peroxybenzoic acid and the benzoic acid, and the peroxybenzoic acid and the benzoic acid enter the rectifying tower for further rectification and purification. The invention removes trace peroxybenzoic acid and benzoic acid in benzaldehyde by using the composite active metal filler in the system filler tower, improves the quality stability of the rectified benzaldehyde product, and ensures that the benzaldehyde product can be stored for a long time without deterioration; and through the cooperation of all devices in the system, the quality of the benzaldehyde is improved, so that the rectified benzaldehyde has low acid value, low color number, high content and no peculiar smell, meets the requirements of food-grade benzaldehyde, is easy to store and has stable quality.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The system is characterized by comprising a packing tower, a buffer chamber at the top of the packing tower, a middle tank communicated with the buffer chamber through a first pipeline and a power assembly, wherein the packing tower is communicated with the buffer chamber; the bottom of the packing tower is provided with a material inlet for inputting benzaldehyde, a packing layer is arranged in the packing tower, and the packing layer comprises composite active metal packing;
the benzaldehyde is powered by the power component, enters the packing tower from the material inlet, passes through the action of the packing layer, reaches the buffer chamber, enters the intermediate tank through the first pipeline, and is finally output by the intermediate tank.
2. The system for efficiently upgrading oxidized benzaldehyde according to claim 1, wherein the composite active metal filler in the filler layer comprises one or more of Zn, mg, al, ca, fe, cu, sn having different particle sizes.
3. The system for efficiently upgrading oxidized benzaldehyde according to claim 2, wherein the composite active metal filler has a particle size of 1-5 mm to ensure that there are sufficient gaps between the fillers for the benzaldehyde material to pass through.
4. The system for efficiently improving the quality of oxidized benzaldehyde according to claim 1, wherein the buffer chamber contains nitrogen, and the buffer chamber is provided with a nitrogen replacement device for removing hydrogen generated after the benzoic acid, peroxybenzoic acid and the composite active metal filler in the benzaldehyde react.
5. The system for efficiently improving the quality of oxidized benzaldehyde according to claim 1, wherein the first pipeline is provided with a U-shaped bent pipe which is bent upwards, and the U-shaped bent pipe is arranged at a position close to the joint of the first pipeline and the buffer chamber.
6. The system for efficiently improving the quality of the oxidized benzaldehyde according to claim 1, wherein a tower body of the packing tower is provided with packing holes, and the packing holes are manholes, so that the composite active metal packing in the packing tower is replaced conveniently.
7. The system for efficiently improving the quality of oxidized benzaldehyde according to claim 1, wherein the first pipeline is provided with a sampling port for detecting the content of peroxide and acid in the sample in real time.
8. The application of the system for efficiently improving the quality of the benzaldehyde by an oxidation method according to any one of claims 1 to 7, which is characterized in that the system for efficiently improving the quality of the benzaldehyde by an oxidation method is arranged between a primary distillation tower and a rectifying tower of a benzaldehyde production device by an oxidation method, benzaldehyde output from the primary distillation tower is continuously transferred into a material inlet at the bottom of a packed tower, is output from a middle tank after being processed by the system, and enters the rectifying tower for continuous rectification and purification, so that the continuous operation of the system for efficiently improving the quality of the benzaldehyde by an oxidation method is realized.
9. A method for efficiently improving the quality of benzaldehyde by an oxidation method is characterized in that the method adopts a system for efficiently improving the quality of benzaldehyde by the oxidation method to treat benzaldehyde output by a primary distillation tower so as to remove peroxide and residual organic acid in the benzaldehyde;
the method comprises the steps of continuously inputting benzaldehyde output from a primary distillation tower into a packing tower, providing power by a power component, enabling the benzaldehyde to enter from a material inlet at the bottom of the packing tower, removing peroxide and residual organic acid from the benzaldehyde under the action of composite active metal packing in a packing layer, enabling the benzaldehyde to reach a buffer chamber, enabling the benzaldehyde to enter a middle tank through a first pipeline, outputting the benzaldehyde from the middle tank, and continuously transferring the benzaldehyde into a rectifying tower for further rectifying and purifying.
10. The method for efficiently improving the quality of oxidized benzaldehyde according to claim 9, wherein the retention time of benzaldehyde in the filler layer is 2 to 4 hours; the buffer chamber adopts a nitrogen replacement device, and nitrogen replacement is carried out on the buffer chamber every 1-3 h.
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| CN113603585A (en) * | 2021-09-23 | 2021-11-05 | 福州大学 | Continuous production process of ultra-pure methyl lactate |
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