CN114874077B - Deodorization method for coking phenol - Google Patents
Deodorization method for coking phenol Download PDFInfo
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- CN114874077B CN114874077B CN202210572830.6A CN202210572830A CN114874077B CN 114874077 B CN114874077 B CN 114874077B CN 202210572830 A CN202210572830 A CN 202210572830A CN 114874077 B CN114874077 B CN 114874077B
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 177
- 238000004939 coking Methods 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 76
- 238000004332 deodorization Methods 0.000 title abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 63
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 58
- 238000004821 distillation Methods 0.000 claims abstract description 53
- 238000005406 washing Methods 0.000 claims abstract description 53
- 230000003647 oxidation Effects 0.000 claims abstract description 52
- 230000001877 deodorizing effect Effects 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 40
- 239000003513 alkali Substances 0.000 claims abstract description 36
- 230000020477 pH reduction Effects 0.000 claims abstract description 21
- 239000007800 oxidant agent Substances 0.000 claims abstract description 17
- 230000009965 odorless effect Effects 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 239000012530 fluid Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 107
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 46
- 239000007788 liquid Substances 0.000 claims description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- 239000012153 distilled water Substances 0.000 claims description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims 5
- 239000008346 aqueous phase Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 22
- 238000007670 refining Methods 0.000 description 21
- 235000011121 sodium hydroxide Nutrition 0.000 description 13
- 239000012535 impurity Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 4
- 239000011280 coal tar Substances 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 235000013599 spices Nutrition 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- -1 alkylphenol Chemical compound 0.000 description 1
- 238000000998 batch distillation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/72—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/86—Purification; separation; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a deodorizing method of coked phenol, which comprises the following steps of (1) acidizing: acidifying the coking phenol raw material and an acid solution to obtain an acidified solution after full acidification; (2) washing with water and separating: washing the acidizing fluid with water under stirring, and standing and layering after washing to obtain an oil phase A; (3) oxidation and alkali washing: adding an oxidant into the oil phase A to obtain a first oxidation solution, and adding an alkali solution into the first oxidation solution after the oxidation is completed to perform alkali washing treatment to obtain a mixed solution; (4) distillation: and (3) heating and distilling the mixed solution obtained in the step (3) to obtain odorless phenol. The deodorization method has the advantages of low equipment investment cost, good economic benefit and suitability for industrial application, and can realize the purpose of deodorizing the coking phenol without adopting a complex rectifying device.
Description
Technical Field
The invention relates to the technical field of post-treatment of chemical products, in particular to a deodorizing method of coked phenol.
Background
Phenol is a white crystal with special odor, is an important organic chemical raw material, is mainly used for producing phenolic resin, caprolactam, bisphenol A, adipic acid, aniline, alkylphenol, salicylic acid and the like, can be used as a solvent, a reagent, a disinfectant and the like, and has very wide application in the aspects of synthetic fibers, synthetic rubber, plastics, medicines, pesticides, spices, dyes, coatings and the like.
Industrial phenols are mainly petroleum phenol (cumene route chemical synthesis) and coking phenol (coal tar extraction) according to source. Coking phenol is obtained by fractionating coal tar, cutting phenolic components in the coking phenol, and further rectifying and purifying, and compared with petroleum phenol, the coking phenol has more price advantage and is widely used. The coking phenol obtained by fractionating coal tar contains impurities with strong odor such as thiophenol, mercaptan, thioether and the like, and has strong malodorous odor, so that the application of the coking phenol is limited, and the coking phenol needs to remove unpleasant malodorous odor impurities so as to better meet the acceptance of downstream industries such as phenolic resin and the like.
The patent publication No. CN1279231A, named as refining method of sulfur-containing crude phenol, discloses two refining methods of sulfur-containing crude phenol, and realizes desulfurization and deodorization of petroleum crude phenol and tar crude phenol. Adding oxidizing agents such as hydrogen peroxide, potassium permanganate, ozone and the like into sulfur-containing crude phenol to fully oxidize mercaptan sulfur, and then performing reduced pressure distillation to obtain refined phenol; the other method is that adding alkali solution such as sodium hydroxide or potassium hydroxide into sulfur-containing crude phenol to dissolve the crude phenol completely in the alkali solution, adding oxidizing agent such as hydrogen peroxide, potassium permanganate, ozone and the like to oxidize mercaptan sulfur sufficiently, separating oil phase and water phase, adding inorganic acid into the water phase to reduce phenolate into phenol, separating oil phase and water phase, and distilling the oil phase to obtain refined phenol. However, the method mainly aims at the purification of phenols directly recovered from light oil or coal tar alkaline residues, has long treatment period and poor deodorization effect, and is not suitable for deodorizing and purifying coking phenol with more complex components.
The patent publication No. CN 101704726A, the name is a continuous refining and separating device and method for coking crude phenol, the continuous refining and separating device for coking crude phenol comprises a primary pretreatment acid adding unit consisting of a static mixer, a primary stirring tank and a scraping film evaporator, a secondary pretreatment oxidation unit consisting of a secondary stirring tank and a buffer tank, a dephenolization slag tower and a rectifying tower system comprising a dehydrating tower, a phenol refining tower, an o-cresol refining tower and a m-cresol refining tower, wherein the rectifying tower system adopts five-stage rectifying towers to decolorize, deodorize, remove impurities and the like for coking phenol raw materials, and the purity of the obtained phenol is up to 99.6%. Although the process for refining and separating the coked crude phenol provided in this patent can obtain phenol of high purity. However, the patent is only practiced in a phenol refining device in the coal gasification industry at present, and the actual application of refining the crude phenol in the coking industry is not yet carried out, the technology of the patent is a technology derived from refining the coal gasification crude phenol, the product quality in the technology of the patent does not break through the level of the existing large-scale treatment device of the coking crude phenol, no report is applied in the production of the coking enterprises, and the whole separation and purification process disclosed by the patent has more equipment and larger equipment investment, and in addition, the separation and purification steps are complicated and complicated, and the final phenol purity can be influenced by the occurrence of any step in the middle.
The patent publication No. CN 105198711A, entitled a refining apparatus and method for coking crude phenol, the refining apparatus disclosed in this patent mainly comprises a crude phenol pre-distillation system, an impurity conversion system and a refining distillation system. The problem of impurity removal is solved by adopting a mercaptan removal catalyst in an adsorption reaction tower of an impurity conversion system, and the addition of a liquid oxidant into raw material crude phenol is avoided, so that the operation is more convenient to control, and the purity of finally obtained phenol can reach 99.9 percent at most. However, the catalyst is expensive and is easily deactivated after a certain period of use, thus resulting in high running costs of the process for refining coked crude phenol in practical industrial applications.
The patent publication No. CN 105949037A, named a method for refining coking crude phenol, comprises the steps of acidifying and oxidizing raw materials of coking crude phenol, rectifying, converting by ion exchange resin, rectifying again, refining again and the like for multiple times, and the purity of phenol is 99.8%. However, the rectification refining unit in the patent is a batch rectifying tower, namely, a batch distillation method of phenol fraction is adopted, so that the whole crude phenol refining process is more complex, and the processing cost of the final product is increased.
Therefore, although the coking crude phenol refining method disclosed in the above patent can obtain high-purity phenol and achieve the effect of deodorizing the coking phenol, a plurality of rectifying devices are required to be arranged in the implementation process, so that the equipment investment is large, the process flow path is long, the production cost is increased, and the operation process is complex. There is a need to develop a method for deodorizing coked phenol with low cost, simple operation and high product purity, which can remove the bad smell in coked phenol and meet the requirements of downstream processes.
Disclosure of Invention
The invention aims to provide a deodorizing method of coking phenol, which solves the problems of high cost, complex operation and insignificant deodorizing effect in the existing refining method of coking crude phenol and meets the requirements of coking industry on high-purity phenol production.
The aim of the invention is achieved by the following technical scheme:
a deodorizing method of coked phenol, comprising the steps of,
(1) Acidifying: acidifying the coking phenol raw material and an acid solution to obtain an acidified solution after full acidification;
(2) Washing and separating: stirring, washing with water, standing and layering after washing is completed to obtain an oil phase A;
(3) Oxidation and alkaline washing: adding an oxidant into the oil phase A to obtain a first oxidation solution, and adding an alkali solution into the first oxidation solution A after the oxidation is completed to perform alkali washing treatment to obtain a mixed solution;
(4) And (3) distilling: and (3) heating and distilling the mixed solution obtained in the step (3) to obtain odorless phenol.
Further, the mixed solution after the alkaline washing treatment in the step (3) is subjected to secondary oxidation before distillation in the step (4), and the specific steps are as follows: standing and layering the mixed solution after alkaline washing treatment to obtain an oil phase B, adding an oxidant into the oil phase B to obtain a second oxidation solution, and heating and distilling the second oxidation solution after oxidation to obtain odorless phenol.
Further, the mass ratio of the acid solution in the step (1) to the coking phenol raw material is 1-3:100, the acidification treatment is carried out under stirring, the stirring time is 1-1.5 h, and the acidification treatment temperature is 40-60 ℃;
preferably, the mass ratio of the acid solution to the coking phenol raw material is 1:100, the acidification stirring time is 1h, the stirring speed is 60rpm, and the acidification temperature is 50 ℃;
more preferably, the acid solution is 98% concentrated sulfuric acid.
Further, the washing operation in the step (2) uses distilled water to wash the acidizing fluid, and the washing process is kept at a constant temperature and stirred for 1h.
Preferably, the distilled water is (0.5-1)/2 of the mass of the coking phenol raw material, and the water washing temperature is kept at a constant temperature of 50 ℃;
more preferably, the distilled water is present in an amount of 1/2 of the mass of the coked phenol feedstock.
Further, the standing delamination operation is performed in a liquid separating device, and the water phase is removed after standing delamination to keep the oil phase.
Further, in the oxidation step, the mass ratio of the oxidant to the coking phenol raw material is 1-3:100, the temperature of the oxidation process is controlled to be 40-60 ℃, and the continuous stirring time of the oxidation process is 1-1.5 h;
preferably, the mass ratio of the oxidant to the coked phenol feedstock is 1:100.
Further, the oxidant is hydrogen peroxide or ozone, the temperature of the oxidation process is controlled to be 50 ℃, the continuous stirring time of the oxidation process is 1h, and the stirring speed is 60rpm.
Preferably, the oxidizing agent is 30% hydrogen peroxide.
Further, the mass ratio of the alkaline solution added into the oxidation liquid A in the step (3) to the coking phenol raw material is 1:10.
Preferably, the alkaline solution is sodium hydroxide solution or sodium bicarbonate solution.
More preferably, the alkaline solution is a 30% sodium hydroxide solution.
Further, the acidification, water washing, oxidation, alkali washing and second oxidation are all carried out in a reaction kettle, and the heating distillation operation is carried out in a distillation device.
Further, a stirring device is arranged in the reaction kettle, the temperature of liquid in the distillation device is 130-140 ℃, the vacuum degree is 98-100kpa, the top temperature of the distillation device is 100-120 ℃, and finally odorless phenol is produced without reflux.
The beneficial effects of the invention are as follows:
1. the deodorizing method for the coking phenol finally obtains the high-purity almost odorless phenol through acidification, water washing and liquid separation, oxidation, alkali washing and liquid separation, secondary oxidation and distillation, the deodorizing purpose of the coking phenol can be achieved only by using a reaction kettle with a stirring device, a liquid separation device and a distillation device in the whole operation process flow, the input cost is low, the deodorizing purpose of the coking phenol can be achieved without adopting a complex rectifying device, and the deodorizing method for the coking phenol has good economic benefit and is suitable for industrial application.
2. The invention provides a deodorizing method of coking phenol, which comprises the steps of adding concentrated sulfuric acid to acidify coking phenol, removing alkaline impurities (such as aniline, etc.) in coking phenol, removing sulfuric acid organic salts, etc. impurities generated by the acidizing treatment by using distilled water, removing odor by utilizing the strong oxidizing property of hydrogen peroxide to react with thiol, thiophenol, etc. containing odor reducing impurities in coking phenol, removing acidic impurities contained in phenol by using sodium hydroxide alkali liquor, and performing secondary oxidation.
Drawings
FIG. 1 is a schematic flow chart of the process for deodorizing coked phenol of the present invention.
Detailed Description
In order to more clearly illustrate the technical scheme of the invention, the specific embodiments are as follows:
in the following examples, 98% concentrated sulfuric acid, 30% hydrogen peroxide, 30% NaHCO 3 And 30% naoh, respectively.
Example 1
As shown in figure 1, the deodorizing flow diagram of the coking phenol of the invention is shown in the specification, and the specific deodorizing method is as follows:
(1) Adding 920g of 95% coking phenol into a reaction kettle, controlling the temperature of the reaction kettle to be 50 ℃, adding 9.2g of 98% concentrated sulfuric acid into the reaction kettle according to the mass ratio of sulfuric acid to coking phenol raw materials of 1:100, keeping the temperature of the reaction kettle constant at 50 ℃, and continuously stirring for 1h;
(2) After the solution in the reaction kettle is fully acidified, 500ml of distilled water is added into the reaction kettle, the temperature of the reaction kettle is kept constant at 50 ℃ and stirred for 1h, the stirred solution is transferred into a liquid separating device for standing and layering, after the solution is fully layered, water phase is separated to keep an oil phase A, and the oil phase A is transferred into the reaction kettle again;
(3) Adding 9.2g of 30% hydrogen peroxide into a reaction kettle according to the mass ratio of the 30% hydrogen peroxide to the coking phenol raw material of 1:100, controlling the temperature of the reaction kettle to be constant at 50 ℃, and continuously stirring for 1h;
after the oxidation reaction is finished, adding 92g of 30% sodium hydroxide into a reaction kettle according to the mass ratio of 30% NaOH alkali liquor to coking phenol raw materials of 1:10, and performing alkali washing on the mixed materials;
transferring the alkaline-washed solution into a liquid separating device, standing for layering, separating a water phase to obtain an oil phase B after full layering, and then adding the oil phase B into a reaction kettle again;
adding 9.2g of 30% hydrogen peroxide into the reaction kettle according to the mass ratio of the 30% hydrogen peroxide to the coking phenol of 1:100, controlling the temperature of the reaction kettle to be constant at 50 ℃, and synchronously stirring for 1h;
(4) Finally, a small feed opening switch valve of the reaction kettle is opened, so that liquid in the reaction kettle enters a distillation device, the temperature of the liquid in the distillation device is 130-140 ℃, the vacuum degree is 98-100kpa, the top temperature of the distillation device is 100-120 ℃, and finally, no backflow is generated to produce almost odorless phenol products.
After the method is subjected to the operation steps of acidification, water washing, oxidation, alkali washing, secondary oxidation and distillation, the odor of the coking phenol is obviously improved, and almost no odor exists.
Judgment criteria for odor of final phenol product:
preliminary evaluation criteria: petroleum phenol is used as a reference substance, three to five laboratory workers smell the petroleum phenol in sequence, and deodorization comparison conclusion is given, and the conclusion is divided into: bad smell improving effect, close smell, same smell, good smell improving effect, and almost no smell.
Determination of deodorizing effect (Shanghai university of applied fragrance detection):
reference standard: GB/T14454.2-20081.10.1
Preparing a sample: standard sample, solvent and fragrance-distinguishing paper
Standard sample: 1) The method selects various spice products which can most represent the current production quality level as standard samples, and when the quality changes, the spice products should be replaced in time, and the standard product in the invention is petroleum phenol. 2) The standard sample is placed in a clean, dry and airtight inert container, filled with nitrogen, stored in a dark place, and prevented from being polluted by aroma.
Operation procedure: in an air-freshening and odor-free fragrance evaluation room, firstly, respectively placing an equivalent sample to be inspected and a standard sample in the same clean and odorless container for fragrance evaluation, comparing fragrance of the bottle mouth, and then respectively evaluating.
The aroma assessment results can be expressed in terms of scores: pure (39.1 to 40.0 minutes), purer (36.0 to 39.0 minutes), acceptable (32.0 to 35.9 minutes), acceptable (28.0 to 31.9 minutes), acceptable (24.0 to 27.9 minutes) and ineligible (24.0 minutes).
Example 2
(1) Adding 950g of 95% coking phenol into a reaction kettle, controlling the temperature of the reaction kettle to be 50 ℃, adding 9.5g of 98% concentrated sulfuric acid into the reaction kettle according to the mass ratio of sulfuric acid to coking phenol raw materials of 1:100, keeping the temperature of the reaction kettle constant at 50 ℃, and continuously stirring for 1h;
(2) After the solution in the reaction kettle is fully acidified, 500ml of distilled water is added into the reaction kettle, the temperature is kept constant at 50 ℃, the mixture is stirred for 1h, the stirred solution is transferred into a liquid separating device for standing and layering, after the mixture is fully layered, water phase is separated to keep an oil phase A, and the oil phase A is transferred into the reaction kettle again;
(3) Adding 9.5g of 30% hydrogen peroxide into a reaction kettle according to the mass ratio of the 30% hydrogen peroxide to the coking phenol raw material of 1:100, controlling the temperature of the reaction kettle to be constant at 50 ℃, and continuously stirring for 1h;
after the oxidation reaction is finished, adding 95g of 30% sodium hydroxide into a reaction kettle according to the mass ratio of 30% NaOH alkali liquor to coking phenol raw materials of 1:10, and performing alkali washing on the mixed materials;
(4) Finally, a discharge port switch valve of the reaction kettle is opened, so that the alkaline-washed solution in the reaction kettle is transferred to a distillation device, the liquid temperature in the distillation device is 130-140 ℃, the vacuum degree is 98-100kpa, the top temperature of the distillation device is 100-120 ℃, and the almost odorless phenol product is finally obtained through heating distillation operation.
After the operation steps of acidification, distilled water extraction, primary oxidation and caustic soda washing, the method has good odor improvement effect on the coking phenol.
The method for detecting the deodorizing effect of the final phenol product was the same as that of example 1.
Example 3
(1) 1050g of 95% coking phenol is put into a reaction kettle, the temperature of the reaction kettle is controlled to be 50 ℃, 10.5g of 98% concentrated sulfuric acid is added into the reaction kettle according to the mass ratio of sulfuric acid to coking phenol raw materials of 1:100, the temperature of the reaction kettle is kept constant at 50 ℃, and stirring is continued for 1h;
(2) After the solution in the reaction kettle is fully acidified, 500ml of distilled water is added into the reaction kettle, the temperature is kept constant at 50 ℃, the mixture is stirred for 1h, the stirred solution is transferred into a liquid separating device for standing and layering, after the mixture is fully layered, water phase is separated to keep an oil phase A, and the oil phase A is transferred into the reaction kettle again;
(3) Adding 10.5g of 30% hydrogen peroxide into a reaction kettle according to the mass ratio of the 30% hydrogen peroxide to the coking phenol raw material of 1:100, controlling the temperature to be constant at 50 ℃, and continuously stirring for 1h;
after completion of the oxidation reaction, 30% NaHCO 3 According to 30% NaHCO 3 The alkali liquor and the coking phenol raw materials are added into the reaction kettle in a mass ratio of 1:10105g of 30% sodium bicarbonate was added and the mixture was alkali washed.
(4) Finally, a discharge port switch valve of the reaction kettle is opened, so that the alkaline-washed solution in the reaction kettle is transferred to a distillation device, the liquid temperature in the distillation device is 130-140 ℃, the vacuum degree is 98-100kpa, the top temperature of the distillation device is 100-120 ℃, and the almost odorless phenol product is finally obtained through heating distillation operation.
After the operation steps of acidification, water washing, oxidation, alkali washing and distillation, the method has good odor improvement effect on the coking phenol.
The method for detecting the deodorizing effect of the final phenol product was the same as that of example 1.
Example 4
(1) Adding 920g of 95% coking phenol into a reaction kettle, controlling the temperature of the reaction kettle to be 50 ℃, adding 27.6g of 98% concentrated sulfuric acid into the reaction kettle according to the mass ratio of sulfuric acid to coking phenol raw materials of 3:100, keeping the temperature of the reaction kettle constant at 50 ℃, and continuously stirring for 1h;
(2) After the solution in the reaction kettle is fully acidified, 250ml of distilled water is added into the reaction kettle, the temperature of the reaction kettle is kept constant at 50 ℃ and stirred for 1h, the stirred solution is transferred into a liquid separating device for standing and layering, after the solution is fully layered, water phase is separated to keep an oil phase A, and the oil phase A is transferred into the reaction kettle again;
(3) Adding 27.6g of 30% hydrogen peroxide into a reaction kettle according to the mass ratio of the 30% hydrogen peroxide to the coking phenol raw material of 3:100, controlling the temperature of the reaction kettle to be constant at 50 ℃, and continuously stirring for 1h;
after the oxidation reaction is finished, adding 92g of 30% sodium hydroxide into a reaction kettle according to the mass ratio of 30% NaOH alkali liquor to coking phenol raw materials of 1:10, and performing alkali washing on the mixed materials;
transferring the alkaline-washed solution into a liquid separating device, standing for layering, separating a water phase to obtain an oil phase B after full layering, and then adding the oil phase B into a reaction kettle again;
adding 9.2g of 30% hydrogen peroxide into the reaction kettle according to the mass ratio of the 30% hydrogen peroxide to the coking phenol of 1:100, controlling the temperature of the reaction kettle to be constant at 50 ℃, and synchronously stirring for 1h;
(4) Finally, a small feed opening switch valve of the reaction kettle is opened, so that liquid in the reaction kettle enters a distillation device, the temperature of the liquid in the distillation device is 130-140 ℃, the vacuum degree is 98-100kpa, the top temperature of the distillation device is 100-120 ℃, and finally, no backflow is generated to produce almost odorless phenol products.
After the method is subjected to the operation steps of acidification, water washing, oxidation, alkali washing, secondary oxidation and distillation, the odor of the coking phenol is obviously improved, and almost no odor exists.
The method for detecting the deodorizing effect of the final phenol product was the same as that of example 1.
Example 5
(1) Adding 920g of 95% coking phenol into a reaction kettle, controlling the temperature of the reaction kettle to be 50 ℃, adding 27.6g of 98% concentrated sulfuric acid into the reaction kettle according to the mass ratio of sulfuric acid to coking phenol raw materials of 3:100, keeping the temperature of the reaction kettle constant at 50 ℃, and continuously stirring for 1h;
(2) After the solution in the reaction kettle is fully acidified, 500ml of distilled water is added into the reaction kettle, the temperature of the reaction kettle is kept constant at 50 ℃ and stirred for 1h, the stirred solution is transferred into a liquid separating device for standing and layering, after the solution is fully layered, water phase is separated to keep an oil phase A, and the oil phase A is transferred into the reaction kettle again;
(3) Adding 9.2g of 30% hydrogen peroxide into a reaction kettle according to the mass ratio of the 30% hydrogen peroxide to the coking phenol raw material of 1:100, controlling the temperature of the reaction kettle to be constant at 50 ℃, and continuously stirring for 1h;
after the oxidation reaction is finished, adding 92g of 30% sodium hydroxide into a reaction kettle according to the mass ratio of 30% NaOH alkali liquor to coking phenol raw materials of 1:10, and performing alkali washing on the mixed materials;
transferring the alkaline-washed solution into a liquid separating device, standing for layering, separating a water phase to obtain an oil phase B after full layering, and then adding the oil phase B into a reaction kettle again;
adding 27.6g of 30% hydrogen peroxide into the reaction kettle according to the mass ratio of the 30% hydrogen peroxide to the coking phenol of 3:100, controlling the temperature of the reaction kettle to be constant at 50 ℃, and synchronously stirring for 1h;
(4) Finally, a small feed opening switch valve of the reaction kettle is opened, so that liquid in the reaction kettle enters a distillation device, the temperature of the liquid in the distillation device is 130-140 ℃, the vacuum degree is 98-100kpa, the top temperature of the distillation device is 100-120 ℃, and finally, no backflow is generated to produce almost odorless phenol products.
After the method is subjected to the operation steps of acidification, water washing, oxidation, alkali washing, secondary oxidation and distillation, the odor of the coking phenol is obviously improved, and almost no odor exists.
The method for detecting the deodorizing effect of the final phenol product was the same as that of example 1.
Comparative example 1: alkali-free washing deodorization method for coking phenol
(1) Adding 950g of 95% coking phenol into a reaction kettle, controlling the temperature of the reaction kettle to be 50 ℃, adding 9.5g of 98% concentrated sulfuric acid into the reaction kettle according to the mass ratio of sulfuric acid to coking phenol raw materials of 1:100, keeping the temperature of the reaction kettle constant at 50 ℃, and continuously stirring for 1h;
(2) After the solution in the reaction kettle is fully acidified, 500ml of distilled water is added into the reaction kettle, the temperature is kept constant at 50 ℃, the mixture is stirred for 1h, the stirred solution is transferred into a liquid separating device for standing and layering, after the mixture is fully layered, water phase is separated to keep an oil phase A, and the oil phase A is transferred into the reaction kettle again;
(3) Adding 9.5g of 30% hydrogen peroxide into a reaction kettle according to the mass ratio of the 30% hydrogen peroxide to the coking phenol raw material of 1:100, controlling the temperature of the reaction kettle to be constant at 50 ℃, and continuously stirring for 1h;
(4) Finally, a discharge port switch valve of the reaction kettle is opened, so that the alkaline-washed solution in the reaction kettle is transferred to a distillation device, the liquid temperature in the distillation device is 130-140 ℃, the vacuum degree is 98-100kpa, the top temperature of the distillation device is 100-120 ℃, and the phenol product is finally obtained through heating distillation operation.
After acidification, water washing, oxidation and distillation, the odor improvement effect of the coking phenol is poor.
The method for detecting the deodorizing effect of the final phenol product was the same as that of example 1.
Comparative example 2: non-water washing and alkali washing deodorization method for coking phenol
(1) Adding 1040g of 95% coking phenol into a reaction kettle, controlling the temperature of the reaction kettle to be 50 ℃, adding 10.4g of 98% concentrated sulfuric acid into the reaction kettle according to the mass ratio of sulfuric acid to coking phenol raw materials of 1:100, keeping the temperature of the reaction kettle constant at 50 ℃, and continuously stirring for 1h;
(2) After the solution in the reaction kettle is fully acidified, adding 10.4g of 30% hydrogen peroxide into the reaction kettle according to the mass ratio of the 30% hydrogen peroxide to the coking phenol raw material of 1:100, controlling the temperature to be constant at 50 ℃, and synchronously stirring for 1h;
(3) Finally, a discharge port switch valve of the reaction kettle is opened, so that the alkaline-washed solution in the reaction kettle is transferred to a distillation device, the liquid temperature in the distillation device is 130-140 ℃, the vacuum degree is 98-100kpa, the top temperature of the distillation device is 100-120 ℃, and the phenol product is finally obtained through heating distillation operation.
After acidification, oxidation and distillation, the odor improvement effect of the coking phenol is poor.
The method for detecting the deodorizing effect of the final phenol product was the same as that of example 1.
Comparative example 3: water-free washing deodorization method for coking phenol
(1) Adding 920g of 95% coking phenol into a reaction kettle, controlling the temperature of the reaction kettle to be 50 ℃, adding 9.2g of 98% concentrated sulfuric acid into the reaction kettle according to the mass ratio of sulfuric acid to coking phenol raw materials of 1:100, keeping the temperature of the reaction kettle constant at 50 ℃, and continuously stirring for 1h;
(2) After the solution in the reaction kettle is fully acidified, adding 9.2g of 30% hydrogen peroxide into the reaction kettle according to the mass ratio of the 30% hydrogen peroxide to the coking phenol raw material of 1:100, controlling the temperature to be constant at 50 ℃, and synchronously stirring for 1h;
after the oxidation reaction is completed, 30％NaHCO 3 According to 30% NaHCO 3 Adding 92g of 30% sodium bicarbonate into a reaction kettle according to the mass ratio of alkali liquor to coking phenol raw materials of 1:10, and performing alkali washing on the mixed materials;
(3) Finally, a discharge port switch valve of the reaction kettle is opened, so that the alkaline-washed solution in the reaction kettle is transferred to a distillation device, the liquid temperature in the distillation device is 130-140 ℃, the vacuum degree is 98-100kpa, the top temperature of the distillation device is 100-120 ℃, and the phenol product is finally obtained through heating distillation operation.
After acidification, oxidation, alkali washing and distillation, the odor improvement effect of the coking phenol is poor.
The method for detecting the deodorizing effect of the final phenol product was the same as that of example 1.
In order to more clearly explain the reagent parameters and deodorizing results added in the deodorizing methods for the focused phenols of examples 1 to 3 and comparative examples 1 to 3, the following table 1 is specifically summarized.
TABLE 1
From the final results of Table 1, it is understood that the deodorizing effect obtained by the acidification, water washing and liquid separation, oxidation, alkali washing and liquid separation, secondary oxidation and distillation method of example 1 in the present invention is best, and the deodorizing effect obtained by the primary oxidation deodorizing method of coked phenol of examples 2 and 3 is also good. Whereas the alkali-free deodorizing method of the coked phenol of comparative example 1, the alkali-free deodorizing method of the coked phenol of comparative example 2, the deodorizing effect of the water-free deodorizing method of the coked phenol of comparative example 3 is relatively poor.
In the course of the deodorizing operation of the coked phenol, although example 4 and example 5 can obtain better deodorizing effect, the amount of the added acid and the amount of the added oxidizing agent are large compared with example 1, and the energy consumption is high.
The foregoing description is directed to the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the invention, and all equivalent changes or modifications made under the technical spirit of the present invention should be construed to fall within the scope of the present invention.
Claims (15)
1. A deodorizing method for coked phenol, characterized by comprising the steps of,
(1) Acidifying: acidifying the coking phenol raw material with an acid solution, and fully acidifying to obtain an acidified solution, wherein the acid solution is 98% concentrated sulfuric acid, and the acidifying temperature is 40-60 ℃;
(2) Washing and separating: washing the acidizing fluid with water under stirring, and standing and layering after washing to obtain an oil phase A;
(3) Oxidation and alkaline washing: adding an oxidant into the oil phase A to obtain a first oxidation solution, and adding an alkali solution into the first oxidation solution after the oxidation is completed to perform alkali washing treatment to obtain a mixed solution;
(4) And (3) distilling: heating and distilling the mixed solution obtained in the step (3) to obtain odorless phenol;
and (3) carrying out secondary oxidation on the mixed solution subjected to alkali washing treatment in the step (3) before distillation in the step (4), wherein the specific steps are as follows: standing and layering the mixed solution after alkaline washing treatment to obtain an oil phase B, adding an oxidant into the oil phase B to obtain a second oxidation solution, and heating and distilling the second oxidation solution after oxidation to obtain odorless phenol;
the temperature of the oxidation process is controlled to be 40-60 ℃, the oxidant is hydrogen peroxide, and the alkali solution is sodium hydroxide solution or sodium bicarbonate solution.
2. The method for deodorizing a coked phenol according to claim 1, wherein the mass ratio of the acid solution in the step (1) to the coked phenol raw material is 1 to 3:100, the acidification treatment is carried out under stirring, and the stirring time is 1-1.5 h.
3. The deodorizing method for a carbonized phenol as set forth in claim 2, wherein the mass ratio of the acid solution to the raw material of the carbonized phenol is 1:100, wherein the stirring time of the acidification treatment is 1h, the stirring speed is 60rpm, and the acidification treatment temperature is 50 ℃.
4. The method for deodorizing a carbonized phenol as set forth in claim 1, wherein the washing operation in the step (2) uses distilled water to wash the acidified solution, and the washing process is maintained at a constant temperature and maintained for 1 hour.
5. The method for deodorizing a carbonized phenol as set forth in claim 4, wherein the distilled water is present in an amount of (0.5-1)/2 based on the mass of the raw material of the carbonized phenol, and the washing temperature is kept at a constant temperature of 50 ℃.
6. The method for deodorizing a coked phenol according to claim 5, wherein the amount of distilled water is 1/2 of the mass of the coked phenol raw material.
7. The method for deodorizing a carbonized phenol as set forth in claim 1, wherein the operation of standing and layering is carried out in a liquid separating apparatus, and the aqueous phase is removed after standing and layering to retain an oil phase.
8. The deodorizing method for a coked phenol as set forth in claim 1, wherein the mass ratio of the oxidizing agent to the coked phenol raw material in the oxidizing step is 1 to 3: and 100, continuously stirring for 1-1.5 h in the oxidation process.
9. The method for deodorizing a coked phenol according to claim 8, wherein the mass ratio of the oxidizing agent to the coked phenol raw material is 1:100.
10. the deodorizing method for coked phenol as set forth in claim 1, wherein the temperature of the oxidation process is controlled to 50 ℃, the oxidation process is performed under stirring for a duration of 1 hour, and the stirring speed is 60rpm.
11. The method for deodorizing coked phenol according to claim 10, wherein the oxidizing agent is 30% hydrogen peroxide.
12. The method for deodorizing a coked phenol according to claim 1, wherein the mass ratio of the alkali solution added to the oxidizing solution a in the step (3) to the coked phenol raw material is 1:10.
13. the method for deodorizing a coked phenol according to claim 12, wherein the alkali solution is a 30% sodium hydroxide solution.
14. The method for deodorizing a coked phenol according to claim 1, wherein the acidification, water washing, oxidation, alkali washing and the second oxidation are performed in a reaction kettle, and the heating distillation operation is performed in a distillation apparatus.
15. The method for deodorizing coked phenol according to claim 14, wherein a stirring device is arranged in the reaction kettle, the liquid temperature in the distillation device is 130-140 ℃, the vacuum degree is 98-100kPa, the top temperature of the distillation device is 100-120 ℃, and finally odorless phenol is produced without reflux.
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