CN118179407A - Continuous treatment method and device for phenol tar - Google Patents
Continuous treatment method and device for phenol tar Download PDFInfo
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- CN118179407A CN118179407A CN202211597865.1A CN202211597865A CN118179407A CN 118179407 A CN118179407 A CN 118179407A CN 202211597865 A CN202211597865 A CN 202211597865A CN 118179407 A CN118179407 A CN 118179407A
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000002156 mixing Methods 0.000 claims abstract description 118
- 239000000463 material Substances 0.000 claims abstract description 52
- 239000000945 filler Substances 0.000 claims abstract description 39
- 238000000926 separation method Methods 0.000 claims abstract description 38
- 238000004581 coalescence Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000003513 alkali Substances 0.000 claims abstract description 23
- 239000002351 wastewater Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 18
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 48
- 239000003921 oil Substances 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 41
- 230000005540 biological transmission Effects 0.000 claims description 17
- 238000007599 discharging Methods 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002283 diesel fuel Substances 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- 238000012856 packing Methods 0.000 claims description 8
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 6
- 238000004523 catalytic cracking Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000005728 strengthening Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 5
- 238000005192 partition Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-UHFFFAOYSA-N 0.000 description 1
- YHZQOKUDQQISEW-UHFFFAOYSA-N 4-Cumylphenol Natural products C1=CC(C(C)C)=CC=C1C1=CC=C(O)C=C1 YHZQOKUDQQISEW-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- XDTRNDKYILNOAP-UHFFFAOYSA-N phenol;propan-2-one Chemical compound CC(C)=O.OC1=CC=CC=C1 XDTRNDKYILNOAP-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005173 quadrupole mass spectroscopy Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0208—Separation of non-miscible liquids by sedimentation
- B01D17/0211—Separation of non-miscible liquids by sedimentation with baffles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J14/00—Chemical processes in general for reacting liquids with liquids; Apparatus specially adapted therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
- B01J19/0066—Stirrers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a continuous treatment method of phenol tar, which sequentially comprises a material mixing unit, a plate-type coalescence-separation unit and a filler coalescence unit according to the treatment sequence, wherein phenol tar, alkali liquor and a mixing auxiliary agent are firstly conveyed to the material mixing unit to realize mixing and reaction, and overflowed to the plate-type coalescence unit through a feeding baffle after the reaction is finished; the plate type coalescing unit mainly comprises a plurality of coalescing plates and a dephenolizing oil recovery device which are vertically arranged, the horizontal direction of the material overflowed to the plate type coalescing oil recovery device contacts with the direction of the coalescing plates, dephenolizing oil is recovered through the dephenolizing oil recovery device, and phenol-containing wastewater is generated and enters the filler coalescing unit for secondary deoiling. The method and the device provided by the invention can realize the efficient mixing reaction and separation of the phenol tar and the alkali liquor, realize the continuous integrated treatment of the phenol tar, improve the oil-water separation efficiency and avoid the need of rectification treatment.
Description
Technical Field
The invention belongs to the technical field of environmental protection waste treatment, and particularly relates to a method and a device for continuously treating phenol tar.
Background
Phenol tar is a byproduct of a phenol/acetone production device by a cumene method, and contains a plurality of substances with high added value, such as phenol, acetophenone, 4-cumylphenol and the like, and the extraction of the components is one of main methods for utilizing the phenol tar.
CN102826963a discloses a method and apparatus for producing p-cumyl phenol by rectifying phenol tar, using phenol tar produced in the process of synthesizing phenol and acetone by cumene method as raw material, extracting p-cumyl phenol by series operation of several rectifying towers, and can make waste use of phenol tar which is originally burnt and pollutes environment, extracting p-cumyl phenol with multi-purpose chemical substance, thereby achieving the purposes of changing waste into valuables and reducing production cost of p-cumyl phenol.
CN113105316a discloses a method for extracting acetophenone and styrene from phenol tar waste liquid, which uses cumene method to produce phenol tar as raw material source, and uses distillation cutting coarse fraction, multi-tower continuous purification and single-tower rectification refining to obtain the product styrene and acetophenone, in which the gas phase portion of the reduced pressure distillation-tower top is divided into 190 deg.c below and 190-250 deg.c, and respectively fed into different rectification towers, the former is passed through 3 series rectification towers to obtain styrene, and the latter is passed through 2 series rectification towers to obtain acetophenone, and the product acetophenone purity is up to above 99%, so that it can meet continuous large-scale industrial production, and implement high added value recycling of dangerous waste.
However, in the above patent, in order to purify different useful components in phenol tar, a rectification method is used, boiling points of partial components are relatively close, and even if a plurality of towers are used in series connection, the components are difficult to completely separate, and the problems of long overall treatment flow and high energy consumption exist in multi-component extraction.
The new technological research of extracting acetophenone from phenol tar (square bond, jin Dongmei, wang Zhongshan, etc. chemical technology, 2017, v.25 (06): 51-53+61) firstly carries out normal pressure primary distillation on phenol tar, then adds dilute sodium hydroxide solution into the primary distillation product, and the obtained sodium phenolate enters into water phase to be separated out by a separating funnel, and the remaining organic phase is subjected to reduced pressure distillation to recover acetophenone therein, thus solving the problems that acetophenone and phenol can form azeotrope, boiling points of the acetophenone and phenol are close under normal pressure, and separation is difficult. However, the method is to remove heavy components from phenol tar through primary distillation under normal pressure, the primary distillation product, namely light components, is treated by adding alkali solution, the primary distillation needs a certain energy consumption, and moreover, the existing two-phase separation device can not thoroughly separate the generated oil phase and water phase, so that the separation efficiency is affected.
CN113831226a discloses a method for recovering phenol and acetophenone from phenol tar, step one, feeding phenol tar discharged from phenol acetone device into separation equipment, discharging light components mainly including phenol and acetophenone, discharging residual phenol tar at bottom of separation equipment; mixing the light component produced in the first step with an alkali solution, then sending the mixture into a first chromatograph, enabling phenol and alkali to react and dissolve in water, discharging an acetophenone-rich component from the upper part of the first chromatograph, and sending the acetophenone-rich component into a rectifying tower for rectifying to obtain an acetophenone product; discharging a phenol-rich solution from the bottom of the first chromatograph; and thirdly, neutralizing the phenol-rich solution produced in the second step with acid in a neutralization tank to be neutral, and then sending the solution into a second chromatograph, wherein the upper part of the second chromatograph is used for discharging crude phenol, and the bottom is used for discharging wastewater. However, the method also carries out separation treatment on phenol tar, the discharged light components mainly comprise phenol and acetophenone, the residual phenol tar at the bottom of the separation equipment is discharged, the problem of incomplete separation exists by adopting conventional separation equipment, and the subsequent separation by adopting a plurality of chromatographs is uneconomical.
Meanwhile, because the viscosity and the residue content of the phenol tar are high, the substances are difficult to directly extract from the phenol tar, CN102633604A adds sulfate as a catalyst in the phenol tar, and simultaneously adds high-temperature solvent oil, and the mixture is stirred and heated, the temperature is firstly increased to 240-260 ℃ for a period of time, so that the catalyst is uniformly and thoroughly dissolved in the phenol tar, and then the temperature is increased to 300-360 ℃ for cracking reaction, thereby obtaining substances containing useful components such as phenol, acetophenone and the like; the high-temperature solvent oil is solvent oil with the boiling range of more than 240 ℃, and the catalyst is ZnSO 4、MgSO4、Fe2(SO4)3、CuSO4 or Al 2(SO4)3; in addition, phenolic substance salts and other unsaturated components exist in the phenol tar, and crystallization blocking phenomenon and coking phenomenon can be generated in the distillation process, so that equipment is corroded and damaged. There are also some studies on the use of existing equipment in refineries, such as CN106675632A, CN106675613a, for the treatment of phenol tar with coker, which, although using different feeding methods, avoids the tar entering the normal operating condition of the furnace, still has coking phenomena.
Disclosure of Invention
Aiming at the defects of long multi-stage rectification flow, high energy consumption, incomplete alkaline washing, difficult oil-water two-phase separation after washing, easy coking in the cooperative treatment of the traditional device and the like in the prior art, the invention provides a continuous treatment method and device for phenol tar. The method and the device provided by the invention can realize the efficient mixing reaction and separation of the phenol tar and the alkali liquor, realize the continuous integrated treatment of the phenol tar, improve the oil-water separation efficiency and avoid the need of rectification treatment.
The invention provides a continuous treatment method of phenol tar, which sequentially comprises a material mixing unit, a plate-type coalescence separation unit and a filler coalescence unit according to a treatment sequence, wherein the plate-type coalescence unit firstly conveys phenol tar, alkali liquor and a mixing auxiliary agent to the material mixing unit, the material mixing unit mainly comprises a mixing wheel disc assembly and a feeding baffle plate, the materials are mixed and reacted through the mixing wheel disc assembly, and overflows to the plate-type coalescence unit through the feeding baffle plate after the reaction is finished; the plate type coalescing unit mainly comprises a plurality of coalescing plates and a dephenolizing oil recoverer which are vertically arranged, the horizontal direction of the material overflowed to the plate type coalescing plate is contacted with the direction of the coalescing plates, dephenolizing oil is recovered through the dephenolizing oil recoverer, phenolic wastewater is generated and enters the filler coalescing unit, the filler coalescing unit mainly comprises a filler plate and a discharging baffle, and the phenolic wastewater is discharged from the lower part of the discharging baffle after being subjected to secondary deoiling through the filler plate.
In the method of the invention, the alkali in the alkali liquor is at least one of sodium hydroxide, potassium hydroxide and the like, and the mass concentration of the alkali liquor is 2.5% -20%, preferably 5% -10%. The alkali liquor is added in a mass ratio of phenol tar to alkali liquor of 1:0.5-5, preferably 1:1-3.
In the method of the invention, the mixing auxiliary agent can be at least one of benzene, toluene, dimethylbenzene, trimethylbenzene, catalytic cracking diesel oil, residual oil hydrogenated diesel oil and the like, and preferably at least one of dimethylbenzene or catalytic cracking diesel oil; the addition amount is that the volume ratio of the phenol tar to the mixing auxiliary agent is 1:1-10, preferably 1:1-2.5.
In the method of the invention, the mixing wheel disc assembly mainly comprises a motor, a transmission shaft, a mixing wheel disc and a stator, wherein the mixing wheel disc is communicated with the motor through the transmission shaft, and the stator is arranged on the outer side of the mixing wheel disc. The mixing wheel disc can adopt a mixing impeller structure described in CN 200410050799.1. The transmission shaft comprises a hollow shaft and a shaft outer sleeve, the hollow shaft penetrates through the mixing wheel disc, a stator is connected below the shaft outer sleeve and is arranged on the outer side of the mixing wheel disc, and a plurality of baffle plates are distributed on the stator.
In the method of the invention, the operation mode of the hybrid wheel disc assembly is as follows: starting the motor, driving the mixing wheel disc to rotate by the transmission shaft, generating negative pressure inside the mixing wheel disc under the action of centrifugal force, sucking the mixed materials at the bottom into the mixing wheel disc through the liquid suction port at the lower part, accelerating, mixing inside the mixing wheel disc, throwing out the wheel disc from the side surface of the mixing wheel disc, then colliding with the stator arranged outside the mixing wheel disc, further strengthening the mixing effect between the materials, accelerating the reaction, and finally flowing out from the gap of the baffle plate on the stator.
In the method, along with the progress of the reaction, materials continuously enter a reaction system, mixed materials overflow to a plate type coalescence-separation unit through a feeding partition plate, a plurality of coalescence plates parallel to each other, preferably 5-15 plates, are vertically arranged in the plate type coalescence-separation unit, a plurality of herringbone inclined plates are arranged in each coalescence plate, and the horizontal direction of the materials is contacted with the direction of the coalescence plates, so that the oil-water separation effect is enhanced.
In the method of the invention, the herringbone sloping plates in the coalescing plate are symmetrically arranged, and the distance between two adjacent sloping plates is 1-100mm, preferably 4-50mm.
In the method of the present invention, the dephenolized oil recovery device may be arranged at any position between the water inlet partition plate and the water outlet partition plate, but should be kept slightly higher than the water outlet.
In the method of the invention, the packing plate is a plate structure with packing inside, and the number of the packing plates is 3-50, preferably 3-10. The filler can be stainless steel balls, fiber bundles, shells or other fillers and specifications commonly used in the oil-water separation process.
In the method, the recovered oil collected by the dephenolized oil recovery device can be used as part of raw materials of a crude oil refining device or used in other recycling modes.
In the method, the phenol tar is a byproduct of a device for producing phenol/acetone by a cumene method, and mainly contains phenol, acetophenone, alcohols, aromatic hydrocarbons and the like, wherein the phenol is not less than 30%, the acetophenone is not less than 20%, and the aromatic hydrocarbons are not less than 40%.
The invention also provides a treatment device for the phenol tar continuous treatment method, which comprises a material mixing unit, a plate type coalescence separation unit and a filler coalescence unit according to the treatment sequence, wherein the material mixing unit mainly comprises a mixing wheel disc assembly and a feeding baffle plate, phenol tar, alkali liquor and a mixing auxiliary agent are firstly conveyed to the material mixing unit for mixing and reaction, and overflows to the plate type coalescence unit through the feeding baffle plate after the reaction is completed; the plate type coalescing unit mainly comprises a plurality of coalescing plates and a dephenolizing oil recoverer which are vertically arranged, the horizontal direction of the material overflowed to the plate type coalescing plate is contacted with the direction of the coalescing plates, dephenolizing oil is recovered through the dephenolizing oil recoverer, phenolic wastewater is generated and enters the filler coalescing unit, the filler coalescing unit mainly comprises a filler plate and a discharging baffle, and the phenolic wastewater is discharged from the lower part of the discharging baffle after being subjected to secondary deoiling through the filler plate.
In the device, the mixing wheel disc assembly mainly comprises a motor, a transmission shaft, a mixing wheel disc and a stator, wherein the mixing wheel disc is communicated with the motor through the transmission shaft, and the stator is arranged on the outer side of the mixing wheel disc. The transmission shaft comprises a hollow shaft and a shaft outer sleeve, the hollow shaft penetrates through the mixing wheel disc, a stator is connected below the shaft outer sleeve and is arranged on the outer side of the mixing wheel disc, and a plurality of baffle plates are distributed on the stator.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, aiming at the characteristics of phenol tar and the defects of the prior treatment technology, the integrated reaction device is sequentially provided with the material mixing unit, the plate type coalescence separation unit and the filler coalescence unit, and through the synergistic effect of the three units, the efficient separation of oil and water is realized, the water content in the recovered oil is obviously reduced, the phenol content in the phenol-containing wastewater is obviously improved, and the subsequent recycling utilization is facilitated.
(2) According to the invention, the mixed auxiliary agent is used in the alkaline washing reaction process, so that the alkali liquor and phenolic substances in the phenol tar are fully reacted, the materials are obviously layered after the reaction, dephenolized oil and phenol-containing wastewater are formed, the oil-water high-efficiency separation is realized, and the problems of black turbidity of a system and low reaction efficiency caused by direct mixing of the phenol tar with the alkali liquor are avoided. Phenol tar does not require pretreatment prior to reaction with lye.
(3) The material mixing unit adopts a mixing component with a specific structure, namely, a mixing wheel disc component is arranged in the reactor, and material flow enters the interior in the tangential direction of the mixing wheel disc, so that on one hand, the formation of internal fluid vortex is avoided, and the arrangement of an anti-vortex baffle is omitted; on the other hand, materials are circulated, mixed and efficiently reacted in the device at the same time, so that the phenol tar is continuously treated, and the treatment efficiency is improved.
(4) According to the invention, the plate type coalescence-separation unit is adopted to treat the mixed material, and the dephenolized oil with smaller density coalesces and rises on the inclined plate, so that the separation of the dephenolized oil and the phenol-containing wastewater is accelerated; the dephenolized oil and the dephenolized wastewater are respectively and automatically discharged from the dephenolized oil recoverer and the discharge port through the arrangement of the dephenolized oil recoverer, the water outlet baffle plate and the discharge port, and the whole process does not need manual operation.
(5) Compared with the continuous rectification method in the prior art, the method has the advantages of short flow, high efficiency and low cost. If acetophenone in dephenolized oil is recovered, the acetophenone can be recovered through a primary rectifying device, and can also be returned to an oil refining device or an oil refining device for further treatment, the phenolic substances in phenolic wastewater have high content, and the phenolic substances can be recovered after neutralization.
Drawings
FIG. 1 is a schematic diagram of a phenol tar treatment process of the present invention;
The device comprises a feeding port 1, a motor 2, a transmission shaft 3, a shaft outer sleeve 4, a hollow shaft 5, a stator 6, a mixing wheel disc 7, a lower liquid suction port 8, a feeding baffle 9, a coalescing plate 10, a dephenolized oil recovery device 11, a packing plate 12, a discharging baffle 13 and a discharging port 14. A1. A material mixing unit, an A2 plate type coalescence-separation unit and an A3 filler coalescence unit.
FIG. 2 is a flow diagram of a hybrid disc assembly and run-time material according to the present invention; wherein A, the materials enter the mixing wheel disc trend, and B, the materials leave the mixing wheel disc trend.
FIG. 3 is a front view of a stator; and 15, baffle plates.
FIG. 4 is a cross-sectional view of a coalescing plate in a plate coalescing separator element; 1011. Sloping plate.
Detailed Description
The technical scheme and effects of the invention are further described below through examples. The embodiments and specific operation procedures are given on the premise of the technical scheme of the invention, but the protection scope of the invention is not limited to the following embodiments.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below, unless otherwise specified, were purchased from conventional biochemical reagent stores.
The phenol tar used in the examples of the present invention was obtained from a phenol/acetone plant in a petrochemical enterprise. The composition of the gas chromatography-mass spectrometry analysis shows that: 23.88% of acetophenone, 10.35% of phenol, 21.77% of cumylphenol, 34.01% of stilbene, 6.74% of methylstyrene and 3.25% of other materials.
The recovered oil components obtained in examples and comparative examples were detected by gas chromatography-mass spectrometry, and the phenol-containing wastewater component was obtained by mass balance of the recovered oil component and the raw material component. The relevant information of the gas chromatography-mass spectrometry equipment is as follows: instrument model: simer-Feier Trace1310 gas chromatograph tandem ISQ7000 single quadrupole mass spectrometry. Column model TG-5MS,30 m.times.0.25 mm.times.0.25. Mu.m. Temperature programming conditions: the temperature is maintained at 40 ℃ for 10 minutes, the temperature is increased from 5 ℃ to 150 ℃ for 1 minute, and the temperature is increased from 10 ℃ to 300 ℃ for 8 minutes. Mass spectrometry conditions: EI source, 15-450amu full scan.
In the embodiment of the invention, the mixing wheel disc adopts the structure of the mixing impeller described in CN 200410050799.1.
The treatment device used in the embodiment of the invention is shown in the attached figure 1, and sequentially comprises a material mixing unit A1, a plate-type coalescence-separation unit A2 and a filler coalescence unit A3 according to the treatment sequence of phenol tar, wherein the material mixing unit A1 mainly comprises a mixing wheel disc assembly and a feeding partition plate 9, the mixing wheel disc assembly mainly comprises a motor 2, a transmission shaft 3, a mixing wheel disc 7 and a stator 6, the mixing wheel disc 7 is communicated with the motor 2 through the transmission shaft 3, the transmission shaft 3 comprises a hollow shaft 5 and a shaft outer sleeve 4, the hollow shaft 5 is connected with the upper part of the mixing wheel disc 7, the stator 6 is connected under the shaft outer sleeve 4, the stator 6 is arranged outside the mixing wheel disc 7, and a plurality of baffle plates are distributed on the stator 6. Firstly, conveying phenol tar, alkali liquor and a mixing auxiliary agent to a material mixing unit A1, enabling the mixture to enter a mixing wheel disc 7 through the bottom of a transmission shaft 3 for mixing and reacting, and overflowing the mixture to a plate-type coalescence-separation unit A2 through a feeding partition 9 after the reaction is finished; the plate type coalescence-separation unit mainly comprises a plurality of coalescence plates 10 and a dephenolized oil recoverer 11 which are vertically arranged, the horizontal direction of the material overflowed to the moment is contacted with the direction of the coalescence plates, dephenolized oil is recovered by the dephenolized oil recoverer 11, phenol-containing wastewater is generated to enter the filler coalescence unit, the filler coalescence unit mainly comprises a filler plate 12 and a discharge baffle 13, the phenol-containing wastewater is discharged from the discharge baffle 13 after being deoiled for the second time by the filler plate 12, and finally the phenol-containing wastewater is discharged through a discharge port 14.
The phenol tar, alkali liquor and mixing auxiliary agent are conveyed to a material mixing unit A1 through a feed inlet 1, a motor is started, a transmission shaft drives a mixing wheel disc to rotate, negative pressure is generated in the mixing wheel disc under the action of centrifugal force, a bottom mixed material is sucked into the mixing wheel disc through a lower liquid suction port (route A in FIG. 2), accelerated and mixed in the mixing wheel disc and is thrown out of the wheel disc from the side surface of the mixing wheel disc (route B in FIG. 2), then the mixing wheel disc collides with a stator arranged outside the mixing wheel disc, the mixing effect among materials is further enhanced, the reaction is accelerated, and finally the mixed material flows out of a baffle plate gap on the stator. Along with the progress of reaction, the material constantly gets into in the reaction system, and the mixture overflows to the board-like coalescence-separation unit through the feeding baffle, is provided with 7 coalescence boards of parallel arrangement perpendicularly in the board-like coalescence-separation unit, is provided with a plurality of "people" swash plate 1011 in every coalescence board, and the distance is 35mm between two adjacent swash plates, and the mixture horizontal direction contacts with coalescence board direction, has strengthened the oil water separation effect. A dephenolized oil recovery device 11 is arranged between the coalescing plate 10 and the packing plate 12, dephenolized oil is discharged from the dephenolized oil recovery device 11, and the obtained dephenolized oil can be further extracted into acetophenone or other valuable components by adopting a rectification method or returned to a petroleum refining device for recycling after distilling and recovering solvent. The filler plates in the filler coalescing unit are of plate-shaped structures with built-in fillers, the number of the filler plates is 5, the fillers are fiber bundles, and the porosity is more than or equal to 95%.
Example 1
The mixing auxiliary agent is dimethylbenzene, and the proportion V (phenol tar) is as follows: v (mixing aid) =1:1, lye is 9.5% sodium hydroxide solution, added in an amount m (phenol tar): m (lye) =1:3.
Example 2
The mixing auxiliary agent used is benzene, the proportion V (phenol tar): v (mixing aid) =1:1.5, lye is 5% sodium hydroxide solution, added in an amount of m (phenol tar): m (lye) =1:1.1.
Example 3
The mixing auxiliary agent used is trimethylbenzene, the proportion V (phenol tar): v (mixing aid) =1:2, lye is 6% potassium hydroxide solution, added in an amount of m (phenol tar): m (lye) =1:4.
Example 4
The mixing auxiliary agent is an equal volume mixed solvent of toluene and benzene, and the proportion V (phenol tar) is as follows: v (mixing aid) =1:2.5, lye is 7% potassium hydroxide solution, added in an amount of m (phenol tar): m (lye) =1:2.
Example 5
The used mixing auxiliary agent is catalytic cracking diesel oil, the proportion V (phenol tar): v (mixing aid) =1:2.5, lye is 7% potassium hydroxide solution, added in an amount of m (phenol tar): m (lye) =1:2.
Example 6
The mixed auxiliary agent is residual oil hydrogenated diesel oil, and the proportion V (phenol tar) is as follows: v (mixing aid) =1:2.5, lye is 7% potassium hydroxide solution, added in an amount of m (phenol tar): m (lye) =1:2.7.
Comparative example 1
The same as in example 1, except that no mixing aid was used. The system is black and turbid, and no obvious layering is found, namely dephenolized oil and phenol-containing wastewater are not generated.
Comparative example 2
The same example differs in that the mixing disk according to the invention is not used, but instead a conventional stirrer is used. The test results are shown in Table 1.
Comparative example 3
The difference from example 1 is that a conventionally used gravity oil-water separator is used instead of the plate type coalescence-separation unit A2 and the filler coalescence-unit A3. The test results are shown in Table 1.
Comparative example 4
The difference is that no coalescing plate is provided as in example 1. The test results are shown in Table 1.
Comparative example 5
The difference is that no filler plate is provided as in example 1. The test results are shown in Table 1.
TABLE 1 dephenolized oil and phenol-containing wastewater acid composition (wt%)
According to the effects of the embodiment and the comparative example, the phenol tar is treated by the phenol tar separator, so that the high-efficiency separation of the recovered oil and the phenol-containing wastewater is realized, and the effect is not ideal due to the lack of any characteristic of the scheme of the invention.
Claims (15)
1. A continuous treatment method of phenol tar is characterized in that: the invention provides a continuous treatment method and a device for phenol tar, which sequentially comprise a material mixing unit, a plate type coalescence separation unit and a filler, wherein the material mixing unit mainly comprises a mixing wheel disc assembly and a feeding baffle plate, the mixing and the reaction of materials are realized through the mixing wheel disc assembly, and the materials overflow to the plate type coalescence unit through the feeding baffle plate after the reaction; the plate type coalescing unit mainly comprises a plurality of coalescing plates and a dephenolizing oil recoverer which are vertically arranged, the horizontal direction of the material overflowed to the plate type coalescing plate is contacted with the direction of the coalescing plates, dephenolizing oil is recovered through the dephenolizing oil recoverer, phenolic wastewater is generated and enters the filler coalescing unit, the filler coalescing unit mainly comprises a filler plate and a discharging baffle, and the phenolic wastewater is discharged from the lower part of the discharging baffle after being subjected to secondary deoiling through the filler plate.
2. The method according to claim 1, characterized in that: the alkali in the alkali liquor is at least one of sodium hydroxide and potassium hydroxide, and the mass concentration of the alkali liquor is 2.5% -20%, preferably 5% -10%.
3. The method according to claim 1 or 2, characterized in that: the addition amount of the alkali liquor is that the mass ratio of the phenol tar to the alkali liquor is 1:0.5-5, preferably 1:1-3.
4. The method according to claim 1, characterized in that: the mixing auxiliary agent is at least one of benzene, toluene, dimethylbenzene, trimethylbenzene, catalytic cracking diesel oil and residual oil hydrogenated diesel oil, and preferably at least one of dimethylbenzene or catalytic cracking diesel oil.
5. The method according to claim 1 or 4, characterized in that: the addition amount of the mixing auxiliary agent is that the volume ratio of the phenol tar to the mixing auxiliary agent is 1:1-10, preferably 1:1-2.5.
6. The method according to claim 1, characterized in that: the mixing wheel disc assembly mainly comprises a motor, a transmission shaft, a mixing wheel disc and a stator, wherein the mixing wheel disc is communicated with the motor through the transmission shaft, and the stator is arranged on the outer side of the mixing wheel disc.
7. The method according to claim 1 or 6, characterized in that: the transmission shaft comprises a hollow shaft and a shaft outer sleeve, the hollow shaft penetrates through the mixing wheel disc, a stator is connected below the shaft outer sleeve and is arranged on the outer side of the mixing wheel disc, and a plurality of baffle plates are distributed on the stator.
8. The method according to claim 1, characterized in that: the operation mode of the hybrid wheel disc assembly is as follows: starting the motor, driving the mixing wheel disc to rotate by the transmission shaft, generating negative pressure inside the mixing wheel disc under the action of centrifugal force, sucking the mixed materials at the bottom into the mixing wheel disc through the liquid suction port at the lower part, accelerating, mixing inside the mixing wheel disc, throwing out the wheel disc from the side surface of the mixing wheel disc, then colliding with the stator arranged outside the mixing wheel disc, further strengthening the mixing effect between the materials, accelerating the reaction, and finally flowing out from the gap of the baffle plate on the stator.
9. The method according to claim 1, characterized in that: along with the progress of reaction, the material continuously gets into in the reaction system, and the mixed material overflows to the board-like coalescence-separation unit through the feeding baffle, is provided with a plurality of coalescence boards that are parallel to each other perpendicularly in the board-like coalescence-separation unit, and is preferential for 5-15, is provided with a plurality of "people" font swash plates in every coalescence board, and the material horizontal direction contacts with coalescence board direction.
10. The method according to claim 1 or 9, characterized in that: the herringbone inclined plates in the coalescing plate are symmetrically arranged, and the distance between two adjacent inclined plates is 1-100mm, preferably 4-50mm.
11. The method according to claim 1, characterized in that: the dephenolized oil recoverer is arranged at any position between the water inlet baffle plate and the water outlet baffle plate, but is kept slightly higher than the water outlet.
12. The method according to claim 1, characterized in that: the packing plate is of a plate-shaped structure with packing built in, and the number of the packing plate is 3-50, preferably 3-10.
13. The method according to claim 1 or 12, characterized in that: the filler is at least one of stainless steel balls, fiber bundles and shells.
14. The method according to claim 1, characterized in that: the phenol tar is a byproduct of a device for producing phenol/acetone by a cumene method, and mainly contains phenol, acetophenone, alcohols and aromatic hydrocarbons, wherein the phenol is not less than 30%, the acetophenone is not less than 20%, and the aromatic hydrocarbons are not less than 40%.
15. A treatment device for the phenol tar continuous treatment method according to any one of claims 1 to 14, which is characterized by comprising a material mixing unit, a plate type coalescence-separation unit and a filler coalescence unit in treatment sequence, wherein the material mixing unit mainly comprises a mixing wheel disc assembly and a feeding baffle plate, phenol tar, alkali liquor and a mixing auxiliary agent are firstly conveyed to the material mixing unit for mixing and reaction, and overflowed to the plate type coalescence unit through the feeding baffle plate after the reaction is completed; the plate type coalescing unit mainly comprises a plurality of coalescing plates and a dephenolizing oil recoverer which are vertically arranged, the horizontal direction of the material overflowed to the plate type coalescing plate is contacted with the direction of the coalescing plates, dephenolizing oil is recovered through the dephenolizing oil recoverer, phenolic wastewater is generated and enters the filler coalescing unit, the filler coalescing unit mainly comprises a filler plate and a discharging baffle, and the phenolic wastewater is discharged from the lower part of the discharging baffle after being subjected to secondary deoiling through the filler plate.
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| CN202211597865.1A CN118179407A (en) | 2022-12-14 | 2022-12-14 | Continuous treatment method and device for phenol tar |
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