CN114874077A - Method for deodorizing coking phenol - Google Patents
Method for deodorizing coking phenol Download PDFInfo
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- CN114874077A CN114874077A CN202210572830.6A CN202210572830A CN114874077A CN 114874077 A CN114874077 A CN 114874077A CN 202210572830 A CN202210572830 A CN 202210572830A CN 114874077 A CN114874077 A CN 114874077A
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- washing
- oxidation
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 238000004939 coking Methods 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims abstract description 70
- 230000001877 deodorizing effect Effects 0.000 title claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 69
- 238000005406 washing Methods 0.000 claims abstract description 61
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 55
- 238000004821 distillation Methods 0.000 claims abstract description 54
- 239000003513 alkali Substances 0.000 claims abstract description 49
- 230000003647 oxidation Effects 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000003756 stirring Methods 0.000 claims abstract description 44
- 239000002994 raw material Substances 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 230000020477 pH reduction Effects 0.000 claims abstract description 32
- 238000004332 deodorization Methods 0.000 claims abstract description 22
- 230000001590 oxidative effect Effects 0.000 claims abstract description 20
- 239000007800 oxidant agent Substances 0.000 claims abstract description 17
- 230000009965 odorless effect Effects 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 239000012530 fluid Substances 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 108
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 58
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims 1
- 230000000717 retained effect Effects 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 38
- 229960002163 hydrogen peroxide Drugs 0.000 description 27
- 239000000047 product Substances 0.000 description 20
- 238000007670 refining Methods 0.000 description 20
- 239000000463 material Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 11
- 239000012535 impurity Substances 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 5
- 239000011280 coal tar Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003205 fragrance Substances 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
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000002309 gasification Methods 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
- 230000002829 reductive effect Effects 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
- 238000012360 testing method Methods 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
- 239000008346 aqueous phase Substances 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
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 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
- 239000002304 perfume Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000013599 spices Nutrition 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
- 238000012546 transfer Methods 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Images
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
Abstract
The invention discloses a deodorization method of coking phenol, which comprises the following steps of (1) acidification: carrying out acidification treatment on the coking phenol raw material and an acid solution, and fully acidifying to obtain an acidified solution; (2) water washing and separation: washing the acidizing fluid with water under stirring, standing and layering after the washing is finished 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 after the oxidation is finished, adding an alkali solution into the first oxidation solution to carry out alkali washing treatment to obtain a mixed solution; (4) and (3) distillation: heating and distilling the mixed liquid obtained in the step (3) to obtain odorless phenol. The deodorization method needs less equipment investment cost, can realize the aim of deodorizing the coking phenol without adopting a complex rectifying device, has good economic benefit, and is suitable for industrial application.
Description
Technical Field
The invention relates to the technical field of chemical product post-treatment, in particular to a method for deodorizing coking 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.
Industrially phenol is mainly classified by its source into petroleum phenol (cumene route chemical synthesis) and coking phenol (coal tar extraction). The coking phenol is obtained by fractionating coal tar, cutting off phenolic components in the coal tar and further rectifying and purifying, has more price advantage compared with petroleum phenol, and is widely used. The coal contains impurity sulfur with different contents, so that coking phenol obtained by fractionating coal tar contains impurities with strong odor, such as thiophenol, mercaptan, thioether and the like, and has strong foul odor, so that the application of the coking phenol is limited, and the coking phenol can better meet the acceptance of downstream industries, such as phenolic resin and the like, by removing the unpleasant foul odor impurities.
The patent publication No. CN1279231A, entitled 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. One method is that oxydol, potassium permanganate, ozone and other oxidant are added into crude phenol containing sulfur to oxidize mercaptan sulfur fully, and then reduced pressure distillation is carried out to obtain refined phenol; the other method is that sodium hydroxide or potassium hydroxide and other alkali solution are added into sulfur-containing crude phenol to dissolve the crude phenol completely in the alkali solution, hydrogen peroxide, potassium permanganate, ozone and other oxidant are added to oxidize mercaptan sulfur fully, oil phase and water phase are separated, inorganic acid is added into the water phase to reduce phenate into phenol, oil phase and water phase are separated, and the oil phase is distilled to obtain refined phenol. However, the method adopted by the patent mainly aims at refining phenols directly recovered from light oil or coal tar alkaline residue, 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 is named as a continuous refining and separating device and a method of coking crude phenol, the continuous refining and separating device of coking crude phenol comprises a primary pretreatment acidification unit consisting of a static mixer, a primary stirring tank and a wiped film evaporator, a secondary pretreatment oxidation unit consisting of a secondary stirring tank and a buffer tank, a dephenolization residue tower and a rectifying tower system comprising a dehydrating tower, a phenol refining tower, an o-cresol refining tower and an m-p-cresol refining tower, wherein the rectifying tower system adopts a five-stage rectifying tower to carry out processes of decoloring, deodorizing, impurity removing and the like on a coking phenol raw material, and the purity of the obtained phenol is 99.6% at most. Although the patent provides a purification and separation method for coking crude phenol that can obtain phenol with high purity. However, the patent is only practiced in a phenol refining device in the coal gasification industry at present, and has no practical application of refining crude phenol in the coking industry, the patent technology is actually a technology derived from refining of coal gasification crude phenol, the product quality in the patent technology does not break through the level of the existing large-scale coking crude phenol treatment device, and no application report is available in the production of coking enterprises.
Patent publication No. CN 105198711A, entitled coking crude phenol refining device and method, the patent publication No. mainly includes crude phenol pre-distillation system, impurity conversion system and refining distillation system. The mercaptan removal catalyst is adopted in an adsorption reaction tower of an impurity conversion system to solve the problem of impurity removal, and a liquid oxidant is prevented from being added into raw material crude phenol, so that the operation is more convenient to control, and the purity of finally obtained phenol can reach 99.9 percent. However, the catalyst is expensive and is easily deactivated after a certain period of use, which results in high running cost of the coking crude phenol refining method in practical industrial application.
The patent publication No. CN 105949037A is named as a coking crude phenol refining method, and the purity of the obtained phenol is 99.8 percent by carrying out acidification, oxidation pretreatment, rectification, ion exchange resin conversion, rectification refining and other multiple rectification operations on the coking crude phenol raw material. However, the rectification and refining unit in the patent is a batch rectification tower, namely a batch distillation method of phenol fractions is adopted, so that the whole crude phenol refining process is relatively complicated, and the processing cost of a final product is increased.
Therefore, although the coking crude phenol refining method disclosed in the above patent can achieve the effect of deodorizing coking phenol while obtaining high-purity phenol, a plurality of rectification devices are required in the implementation process, the equipment investment is large, the process flow route is long, the production cost is increased, and the operation process is complicated. The method for deodorizing the coking phenol with low cost, simple operation and high product purity needs to be developed urgently, the unpleasant odor in the coking phenol is removed, and the requirements of downstream processes are met.
Disclosure of Invention
The invention aims to provide a coking phenol deodorization method, which solves the problems of high cost, complex operation and unobvious deodorization effect in the existing coking crude phenol refining method and meets the requirement of coking industry on production of high-purity phenol.
The purpose of the invention is realized by the following technical scheme:
a method for deodorizing coking phenol, comprising the steps of,
(1) acidifying: carrying out acidification treatment on the coking phenol raw material and an acid solution, and fully acidifying to obtain an acidified solution;
(2) water washing and separation: stirring, washing with water, standing and layering after washing with water 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 after the oxidation is finished, adding an alkali solution into the first oxidation solution A to perform alkali washing treatment to obtain a mixed solution;
(4) and (3) distillation: heating and distilling the mixed liquid obtained in the step (3) to obtain odorless phenol.
Further, before distillation in step (4), performing second oxidation on the mixed solution subjected to alkali washing treatment in step (3), specifically comprising the following steps: standing and layering the mixed solution after the alkali washing treatment to obtain an oil phase B, adding an oxidant into the oil phase B to obtain a second oxidizing solution, and heating and distilling the second oxidizing solution after the 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 for 1-1.5 hours, 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 acidification liquid is washed by distilled water in the washing operation in the step (2), and the washing process is kept at a constant temperature and is kept stirring for 1 hour.
Preferably, the amount of 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 amount of distilled water is 1/2 of the mass of the coked phenol feedstock.
Further, the standing layering operation is carried out in a liquid separating device, and after standing layering, an aqueous phase is removed, and an oil phase is reserved.
Further, the mass ratio of the oxidant to the coking phenol raw material in the oxidation step is 1-3: 100, the temperature in the oxidation process is controlled to be 40-60 ℃, and the continuous stirring time in the oxidation process is 1-1.5 hours;
preferably, the mass ratio of the oxidant to the coking phenol feedstock is 1: 100.
Further, the oxidant is hydrogen peroxide or ozone, the temperature in the oxidation process is controlled to be 50 ℃, the continuous stirring time in the oxidation process is 1h, and the stirring speed is 60 rpm.
Preferably, the oxidizing agent is 30% hydrogen peroxide.
Further, the mass ratio of the alkali solution added into the oxidation liquid A in the step (3) to the coking phenol raw material is 1: 10.
Preferably, the alkali solution is a sodium hydroxide solution or a sodium bicarbonate solution.
More preferably, the alkali solution is a 30% sodium hydroxide solution.
Further, the acidification, the water washing, the oxidation, the alkali washing and the 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-.
The invention has the beneficial effects that:
1. the method for deodorizing the coking phenol provided by the invention can finally obtain the high-purity almost odorless phenol by acidification, water washing and liquid separation, oxidation, alkali washing and liquid separation, secondary oxidation and distillation, can achieve the aim of deodorizing the coking phenol by only using a reaction kettle, a liquid separation device and a distillation device which are provided with a stirring device in the whole operation process flow, has low input cost, can realize the aim of deodorizing the coking phenol without adopting a complicated rectification device, has good economic benefit, and is suitable for industrial application.
2. The invention provides a coking phenol deodorization method, which comprises the steps of adding concentrated sulfuric acid to coking phenol for acidification treatment in the acidification operation, removing alkaline impurities (such as aniline and the like) in the coking phenol, removing impurities such as organic salts of sulfuric acid and the like generated by the acidification treatment by using distilled water, removing odor by using the strong oxidizing property of hydrogen peroxide to react with odor-containing reductive impurities such as mercaptan, thiophenol and the like in the coking phenol, and performing secondary oxidation after removing acidic impurities contained in the phenol by using sodium hydroxide alkali liquor.
Drawings
FIG. 1 is a schematic flow diagram of a coker phenol deodorization process of the present invention.
Detailed Description
In order to more clearly illustrate the technical solution of the present invention, the following specific embodiments are described:
in the following examples 98% concentrated sulfuric acid, 30% hydrogen peroxide, 30% NaHCO 3 And 30% NaOH are the mass fraction.
Example 1
As shown in the attached figure 1, the deodorization process schematic diagram of the coking phenol of the invention comprises the following steps:
(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 1: 100 of sulfuric acid to coking phenol raw materials, keeping the temperature of the reaction kettle constant at 50 ℃, and continuously stirring for 1 hour;
(2) after the solution in the reaction kettle is sufficiently acidified, adding 500ml of distilled water into the reaction kettle, keeping the temperature of the reaction kettle at 50 ℃ constant, stirring for 1h, transferring the stirred solution into a liquid separating device, standing for layering, after the solution is sufficiently layered, removing a water phase, retaining an oil phase A, and transferring the oil phase A into the reaction kettle;
(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 1 h;
after the oxidation reaction is finished, adding 92g of 30% NaOH into a reaction kettle according to the mass ratio of 30% NaOH alkali liquor to coking phenol raw material of 1: 10, and carrying out alkali washing on the mixed material;
transferring the solution after alkali washing to a liquid separating device, standing for layering, after full layering, removing the water phase to obtain an oil phase B, and then adding the oil phase B into the reaction kettle again;
adding 9.2g of 30% hydrogen peroxide into the reaction kettle according to the mass ratio of 1: 100 of 30% hydrogen peroxide to coking phenol, controlling the temperature of the reaction kettle to be constant at 50 ℃, and synchronously stirring for 1 h;
(4) and finally opening a small material opening switch valve of the reaction kettle, so that the liquid in the reaction kettle enters a distillation device, wherein the temperature of the liquid in the distillation device is 140 ℃ plus materials, the vacuum degree is 98-100kpa, the top temperature of the distillation device is 100 plus materials and 120 ℃, and finally, the almost odorless phenol product is extracted without backflow.
The method is characterized in that after 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.
Evaluation criteria for final phenol product odor:
and (3) preliminary evaluation criteria: petroleum phenol is used as a reference substance, three to five experimenters smell the petroleum phenol in turn, and a deodorization comparison conclusion is given, and the conclusion is divided into: bad odor improving effect, similar odor, same odor, good odor improving effect, and almost no odor.
Determination of deodorizing Effect (fragrance discrimination test by Shanghai university of application):
reference standard: GB/T14454.2-20081.10.1
Preparing a sample: standard sample, solvent and fragrance identification paper
Standard samples: 1) selecting various perfume products which can represent the current production quality level best as standard samples, and replacing the standard samples in time when the quality changes, wherein the standard sample in the invention is petroleum phenol. 2) And (3) placing the standard sample in a clean, dry and closed inert container, filling (or filling nitrogen), and storing in dark to prevent fragrance pollution.
The operation procedure is as follows: in an air-refreshing and unpurified aroma evaluation room, an equal amount of a test sample to be tested and a standard sample are respectively put in the same, clean and odorless container for evaluation of aroma, including comparison of aroma of a bottle mouth, and then evaluation is respectively carried out.
The aroma assessment results may be expressed in scores: pure (39.1 to 40.0 minutes), pure (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 not acceptable (24.0 minutes).
Example 2
(1) Putting 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 1: 100 of sulfuric acid to coking phenol raw materials, keeping the temperature of the reaction kettle constant at 50 ℃, and continuously stirring for 1 hour;
(2) after the solution in the reaction kettle is sufficiently acidified, adding 500ml of distilled water into the reaction kettle, keeping the temperature at 50 ℃ constant, stirring for 1h, transferring the stirred solution into a liquid separating device, standing for layering, after the solution is sufficiently layered, removing a water phase to retain an oil phase A, and transferring the oil phase A into the reaction kettle;
(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 1 h;
after the oxidation reaction is finished, adding 95g of 30% NaOH into a reaction kettle according to the mass ratio of 30% NaOH alkali liquor to the coking phenol raw material of 1: 10, and carrying out alkali washing on the mixed material;
(4) and finally opening a discharge port switch valve of the reaction kettle, so that the solution after the alkali washing in the reaction kettle is transferred into a distillation device, wherein 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 the almost odorless phenol product is obtained through heating distillation operation.
The method has good odor improvement effect of the coking phenol after the operation steps of acidification, distilled water extraction, primary oxidation and sodium hydroxide alkaline washing.
The deodorizing effect of the final phenol product was measured by the same method as in 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 1: 100 of sulfuric acid to coking phenol raw material, the temperature of the reaction kettle is kept constant at 50 ℃, and the mixture is continuously stirred for 1 hour;
(2) after the solution in the reaction kettle is sufficiently acidified, adding 500ml of distilled water into the reaction kettle, keeping the temperature at 50 ℃ constant, stirring for 1h, transferring the stirred solution into a liquid separating device, standing for layering, after the solution is sufficiently layered, removing a water phase to retain an oil phase A, and transferring the oil phase A into the reaction kettle;
(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 1 h;
after the oxidation reaction is complete, 30% NaHCO is added 3 According to 30% NaHCO 3 Adding 105g of 30% sodium bicarbonate into a reaction kettle according to the mass ratio of the alkali liquor to the coking phenol raw material of 1: 10, and carrying out alkali washing on the mixed material.
(4) And finally opening a discharge port switch valve of the reaction kettle to transfer the solution after the alkali washing in the reaction kettle to a distillation device, wherein 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 obtaining the almost odorless phenol product through heating distillation operation.
The method has good odor improvement effect of the coking phenol after the operation steps of acidification, water washing, oxidation, alkali washing and distillation.
The deodorizing effect of the final phenol product was measured by the same method as in 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 3: 100 of sulfuric acid to coking phenol raw materials, keeping the temperature of the reaction kettle constant at 50 ℃, and continuously stirring for 1 h;
(2) adding 250ml of distilled water into the reaction kettle after the solution in the reaction kettle is sufficiently acidified, keeping the temperature of the reaction kettle at 50 ℃ constant, stirring for 1h, transferring the stirred solution into a liquid separating device, standing for layering, after the solution is sufficiently layered, removing a water phase, retaining an oil phase A, and transferring the oil phase A into the reaction kettle;
(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 1 h;
after the oxidation reaction is finished, adding 92g of 30% NaOH into a reaction kettle according to the mass ratio of 30% NaOH alkali liquor to coking phenol raw material of 1: 10, and carrying out alkali washing on the mixed material;
transferring the solution after alkali washing to a liquid separating device, standing for layering, after full layering, removing the water phase to obtain an oil phase B, and then adding the oil phase B into the reaction kettle again;
adding 9.2g of 30% hydrogen peroxide into the reaction kettle according to the mass ratio of 1: 100 of 30% hydrogen peroxide to coking phenol, controlling the temperature of the reaction kettle to be constant at 50 ℃, and synchronously stirring for 1 h;
(4) and finally opening a small material opening switch valve of the reaction kettle, so that the liquid in the reaction kettle enters a distillation device, wherein the temperature of the liquid in the distillation device is 140 ℃ plus materials, the vacuum degree is 98-100kpa, the top temperature of the distillation device is 100 plus materials and 120 ℃, and finally, the almost odorless phenol product is extracted without backflow.
The method is characterized in that after 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 deodorizing effect of the final phenol product was measured by the same method as in 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 3: 100 of sulfuric acid to coking phenol raw materials, keeping the temperature of the reaction kettle constant at 50 ℃, and continuously stirring for 1 h;
(2) after the solution in the reaction kettle is sufficiently acidified, adding 500ml of distilled water into the reaction kettle, keeping the temperature of the reaction kettle at 50 ℃ constant, stirring for 1h, transferring the stirred solution into a liquid separating device, standing for layering, after the solution is sufficiently layered, removing a water phase, retaining an oil phase A, and transferring the oil phase A into the reaction kettle;
(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 1 h;
after the oxidation reaction is finished, adding 92g of 30% NaOH into a reaction kettle according to the mass ratio of 30% NaOH alkali liquor to coking phenol raw material of 1: 10, and carrying out alkali washing on the mixed material;
transferring the solution after alkali washing to a liquid separating device, standing for layering, after full layering, removing the water phase to obtain an oil phase B, and then adding the oil phase B into the reaction kettle again;
adding 27.6g of 30% hydrogen peroxide into the reaction kettle according to the mass ratio of 3: 100 of 30% hydrogen peroxide to coking phenol, controlling the temperature of the reaction kettle to be constant at 50 ℃, and synchronously stirring for 1 hour;
(4) and finally opening a small material opening switch valve of the reaction kettle, so that the liquid in the reaction kettle enters a distillation device, wherein the temperature of the liquid in the distillation device is 140 ℃ plus materials, the vacuum degree is 98-100kpa, the top temperature of the distillation device is 100 plus materials and 120 ℃, and finally, the almost odorless phenol product is extracted without backflow.
The method is characterized in that after 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 deodorizing effect of the final phenol product was measured by the same method as in example 1.
Comparative example 1: alkali-free washing deodorization method for coking phenol
(1) Putting 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 1: 100 of sulfuric acid to coking phenol raw materials, keeping the temperature of the reaction kettle constant at 50 ℃, and continuously stirring for 1 hour;
(2) after the solution in the reaction kettle is sufficiently acidified, adding 500ml of distilled water into the reaction kettle, keeping the temperature at 50 ℃ constant, stirring for 1h, transferring the stirred solution into a liquid separating device, standing for layering, after the solution is sufficiently layered, removing a water phase to retain an oil phase A, and transferring the oil phase A into the reaction kettle;
(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 1 h;
(4) and finally opening a discharge port switch valve of the reaction kettle, so that the solution after the alkali washing in the reaction kettle is transferred into a distillation device, wherein 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 deodorizing effect of the final phenol product was measured by the same method as in example 1.
Comparative example 2: washing-free and alkali washing deodorization method for coking phenol
(1) 1040g of 95% coking phenol is put into a reaction kettle, the temperature of the reaction kettle is controlled to be 50 ℃, 10.4g of 98% concentrated sulfuric acid is added into the reaction kettle according to the mass ratio of 1: 100 of sulfuric acid to coking phenol raw material, the temperature of the reaction kettle is kept constant at 50 ℃, and the mixture is continuously stirred for 1 hour;
(2) after the solution in the reaction kettle is sufficiently acidified, 10.4g of 30% hydrogen peroxide is added into the reaction kettle according to the mass ratio of 1: 100 of the 30% hydrogen peroxide to the coking phenol raw material, the temperature is controlled to be constant at 50 ℃, and the mixture is synchronously stirred for 1 hour;
(3) and finally opening a discharge port switch valve of the reaction kettle, so that the solution after the alkali washing in the reaction kettle is transferred into a distillation device, wherein 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 deodorizing effect of the final phenol product was measured by the same method as in 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 1: 100 of sulfuric acid to coking phenol raw materials, keeping the temperature of the reaction kettle constant at 50 ℃, and continuously stirring for 1 hour;
(2) after the solution in the reaction kettle is sufficiently acidified, 9.2g of 30% hydrogen peroxide is added into the reaction kettle according to the mass ratio of 1: 100 of the 30% hydrogen peroxide to the coking phenol raw material, the temperature is controlled to be constant at 50 ℃, and the mixture is synchronously stirred for 1 hour;
after the oxidation reaction is completed, 30% NaHCO is added 3 According to 30% NaHCO 3 Adding 92g of 30% sodium bicarbonate into a reaction kettle according to the mass ratio of the alkali liquor to the coking phenol raw material of 1: 10, and carrying out alkali washing on the mixed material;
(3) and finally opening a discharge port switch valve of the reaction kettle, so that the solution after the alkali washing in the reaction kettle is transferred into a distillation device, wherein 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 deodorizing effect of the final phenol product was measured by the same method as in example 1.
In order to more clearly illustrate the parameters of the reagents and the deodorization results added in the deodorization methods for phenol in 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 above, it is understood that the deodorizing effect obtained by the method of acidification, water washing and liquid separation, oxidation, alkali washing and liquid separation, secondary oxidation and distillation of example 1 is the best in the present invention, and that the deodorizing effect obtained by the method of primary oxidation of coking phenol of example 2 and example 3 is also excellent. The alkali-washing-free deodorization method of coking phenol in comparative example 1, the alkali-washing-free deodorization method of coking phenol in comparative example 2 and the alkali-washing-free deodorization method of coking phenol in comparative example 3 have relatively poor deodorization effects.
Although examples 4 and 5 can achieve a better deodorizing effect during the coking phenol deodorizing operation, the amount of acid and oxidant added is large and the energy consumption is high compared to example 1.
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.
Claims (10)
1. A method for deodorizing coking phenol, characterized by comprising the steps of,
(1) acidifying: carrying out acidification treatment on a coking phenol raw material and an acid solution, and obtaining an acidification solution after full acidification;
(2) water washing and separation: washing the acidizing fluid with water under stirring, standing and layering after the washing is finished 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 after the oxidation is finished, adding an alkali solution into the first oxidation solution to carry out alkali washing treatment to obtain a mixed solution;
(4) and (3) distillation: heating and distilling the mixed liquid obtained in the step (3) to obtain odorless phenol.
2. The coking phenol deodorization method according to claim 1, characterized in that the mixed solution after the alkali washing treatment in the step (3) is subjected to a second oxidation before the distillation in the step (4), and the specific steps are as follows: standing and layering the mixed solution after the alkali washing treatment to obtain an oil phase B, adding an oxidant into the oil phase B to obtain a second oxidizing solution, and heating and distilling the second oxidizing solution after the oxidation to obtain odorless phenol.
3. The coking phenol deodorization method according to claim 1, characterized in that the mass ratio of the acid solution in the step (1) to the coking phenol raw material is 1-3: 100, carrying out acidification treatment under stirring for 1-1.5 h, wherein the acidification treatment temperature is 40-60 ℃;
preferably, the mass ratio of the acid solution to the coking phenol feedstock is 1: 100, wherein the acidification treatment stirring time is 1h, the stirring speed is 60rpm, and the acidification treatment temperature is 50 ℃;
more preferably, the acid solution is 98% concentrated sulfuric acid.
4. The coking phenol deodorization method according to claim 1, characterized in that the washing operation in the step (2) uses distilled water to wash the acidification solution, the washing process is constant in temperature and is kept stirring for 1 hour;
preferably, the amount of 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 amount of distilled water is 1/2 of the mass of the coked phenol feedstock.
5. The method for deodorizing coking phenol according to claim 1 or 2, wherein said operation of standing and layering is carried out in a liquid separating device, and after standing and layering, the water phase is removed and the oil phase is retained.
6. The method for deodorizing coking phenol according to claim 1 or 2, characterized in that the mass ratio of the oxidizing agent to the coking phenol raw material in said oxidation step is 1 to 3: 100, controlling the temperature in the oxidation process to be 40-60 ℃, and continuously stirring for 1-1.5 h in the oxidation process;
preferably, the mass ratio of the oxidant to the coking phenol feedstock is 1: 100.
7. the method of deodorizing coking phenols according to claim 1, wherein said oxidizing agent is hydrogen peroxide or ozone;
preferably, the temperature of the oxidation process is controlled to be 50 ℃, the oxidation process is carried out under stirring, the continuous stirring time is 1h, and the stirring speed is 60 rpm;
preferably, the oxidizing agent is 30% hydrogen peroxide.
8. The method for deodorizing coking phenol according to claim 1, wherein the mass ratio of the alkali solution added to the oxidation liquid a in said step (3) to the coking phenol raw material is 1: 10;
preferably, the alkali solution is a sodium hydroxide solution or a sodium bicarbonate solution;
more preferably, the alkali solution is a 30% sodium hydroxide solution.
9. The method for deodorizing coking phenols according to claim 1 or 2, wherein said acidifying, washing with water, oxidizing, washing with alkali and second oxidizing are carried out in a reaction vessel, and said heating distillation operation is carried out in a distillation apparatus.
10. The method as claimed in claim 9, wherein the reaction kettle is equipped with a stirring 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 the odorless phenol is extracted without reflux.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08281050A (en) * | 1995-04-11 | 1996-10-29 | Nippon Polyester Kk | Deodorizing method |
| CN1279231A (en) * | 1999-06-30 | 2001-01-10 | 中国石油化工集团公司 | Process for refining coarse phenol containing sulfur |
| JP2007223945A (en) * | 2006-02-23 | 2007-09-06 | Mitsui Chemicals Inc | Method for purifying recovered phenols |
| EP1847522A1 (en) * | 2006-04-18 | 2007-10-24 | INEOS Phenol GmbH & Co. KG | Process for removal of hydroxyacetone from phenol |
| CN104164251A (en) * | 2014-08-28 | 2014-11-26 | 刘五连 | Environment-friendly fuel oil for special car |
| CN105198711A (en) * | 2014-06-27 | 2015-12-30 | 上海宝钢化工有限公司 | Coked crude phenol refining device and method |
| CN105949037A (en) * | 2016-03-23 | 2016-09-21 | 中国科学院过程工程研究所 | Refining method of crude phenol from coking |
| CN111876200A (en) * | 2020-07-30 | 2020-11-03 | 武汉科林化工集团有限公司 | Normal-temperature desulfurization and deodorization process for naphtha |
| CN111892484A (en) * | 2020-05-27 | 2020-11-06 | 河北诚江医药科技有限公司 | Continuous decolorizing and deodorizing method for low-temperature crude phenol in coal gasification |
-
2022
- 2022-05-24 CN CN202210572830.6A patent/CN114874077B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08281050A (en) * | 1995-04-11 | 1996-10-29 | Nippon Polyester Kk | Deodorizing method |
| CN1279231A (en) * | 1999-06-30 | 2001-01-10 | 中国石油化工集团公司 | Process for refining coarse phenol containing sulfur |
| JP2007223945A (en) * | 2006-02-23 | 2007-09-06 | Mitsui Chemicals Inc | Method for purifying recovered phenols |
| EP1847522A1 (en) * | 2006-04-18 | 2007-10-24 | INEOS Phenol GmbH & Co. KG | Process for removal of hydroxyacetone from phenol |
| CN105198711A (en) * | 2014-06-27 | 2015-12-30 | 上海宝钢化工有限公司 | Coked crude phenol refining device and method |
| CN104164251A (en) * | 2014-08-28 | 2014-11-26 | 刘五连 | Environment-friendly fuel oil for special car |
| CN105949037A (en) * | 2016-03-23 | 2016-09-21 | 中国科学院过程工程研究所 | Refining method of crude phenol from coking |
| CN111892484A (en) * | 2020-05-27 | 2020-11-06 | 河北诚江医药科技有限公司 | Continuous decolorizing and deodorizing method for low-temperature crude phenol in coal gasification |
| CN111876200A (en) * | 2020-07-30 | 2020-11-03 | 武汉科林化工集团有限公司 | Normal-temperature desulfurization and deodorization process for naphtha |
Non-Patent Citations (1)
| Title |
|---|
| 李世宏等: "焦化粗酚加工的技术改进及工艺控制", 《辽宁化工》, vol. 39, no. 10, pages 1053 - 1054 * |
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