CN109133241B - FU type composite extractant suitable for coal tar hydrogenation wastewater treatment and application of FU type composite extractant in coal tar hydrogenation wastewater treatment - Google Patents
FU type composite extractant suitable for coal tar hydrogenation wastewater treatment and application of FU type composite extractant in coal tar hydrogenation wastewater treatment Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 74
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 65
- 239000011280 coal tar Substances 0.000 title claims abstract description 55
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 47
- 238000011084 recovery Methods 0.000 claims abstract description 93
- 230000009615 deamination Effects 0.000 claims abstract description 70
- 238000006481 deamination reaction Methods 0.000 claims abstract description 70
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 14
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 161
- 238000000605 extraction Methods 0.000 claims description 128
- 239000002351 wastewater Substances 0.000 claims description 109
- 239000000203 mixture Substances 0.000 claims description 44
- 238000010992 reflux Methods 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000012856 packing Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 229920006395 saturated elastomer Polymers 0.000 claims description 15
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 13
- 239000011269 tar Substances 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 11
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 abstract description 8
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 abstract description 7
- XABJJJZIQNZSIM-UHFFFAOYSA-N azane;phenol Chemical compound [NH4+].[O-]C1=CC=CC=C1 XABJJJZIQNZSIM-UHFFFAOYSA-N 0.000 abstract 1
- 239000000945 filler Substances 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 15
- 230000008569 process Effects 0.000 description 14
- 239000002904 solvent Substances 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 230000008878 coupling Effects 0.000 description 7
- 238000010168 coupling process Methods 0.000 description 7
- 238000005859 coupling reaction Methods 0.000 description 7
- 238000007670 refining Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 150000008442 polyphenolic compounds Chemical class 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- -1 tributyl phosphate compound Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 2
- 229940031826 phenolate Drugs 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/10—Treatment of water, waste water, or sewage by heating by distillation or evaporation by direct contact with a particulate solid or with a fluid, as a heat transfer medium
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Physical Water Treatments (AREA)
- Extraction Or Liquid Replacement (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an FU type composite extractant suitable for coal tar hydrogenation wastewater treatment and application thereof in the aspect of coal tar hydrogenation wastewater treatment, wherein the extractant comprises 60-80 wt% of amine complexing agent, 10-15 wt% of MIBK, 6-8 wt% of isopropyl ether and the balance of other benzene substances, and the extractant is matched with the multifunctional composite tower hydrogenation wastewater treatment device to realize deacidification, deamination, dephenolization and phenol ammonia recovery in a single tower.
Description
Technical Field
The invention belongs to the technical field of coal tar hydrogenation wastewater treatment, and particularly relates to an FU type composite extractant suitable for coal tar hydrogenation wastewater treatment and application of the FU type composite extractant in the aspect of coal tar hydrogenation wastewater treatment.
Background
In recent years, technological researches on production of products such as diesel oil, naphtha and liquefied petroleum gas with high added value by hydro-upgrading using coal tar or fractions thereof as raw materials have been attracting a lot of attention. Although the gradual industrialization of coal tar hydrogenation technology realizes the deep processing of coal tar to a certain extent, and economic benefits are obtained through the converted products, a certain degree of environmental pollution exists in the implementation process of the project. The wastewater in this process can be broadly divided into two categories: oily wastewater and acidic wastewater. The oily wastewater mainly comes from oily wastewater generated by a liquid separating tank of a coke oven gas compression and pretreatment working section; deoxygenated water generated by the hydrogen purification partial deoxygenation tower: oily wastewater generated by a vacuum pumping system of a hydrogenation pretreatment working section: and refining the wastewater generated by the product oil through a dehydrator. The acidic wastewater mainly comes from a cold high-pressure separator of a hydrofining working section, the acidic wastewater is separated from a high-pressure separator and a low-pressure separator of a hydrocracking working section, and the acidic wastewater is separated from a reflux tank at the top of a prefractionator.
The water quality of the coal tar hydrogenation wastewater is characterized in that the wastewater contains phenol and oil in high concentration, and the pollutants in the wastewater are mainly organic pollutants including phenols, ammonia nitrogen, oil substances and the like. The components are extremely complex and difficult to handle. The phenol content in water exceeds 15000mg/L, the oil content exceeds 4000mg/L, and the ammonia nitrogen content 7200mg/L, COD reaches 100000 mg/L.
The acid gas in the wastewater can interfere the treatment process, cause equipment corrosion and scaling, and the ammonia has the effects of microorganism inhibition and subsequent biochemical treatment. Chemical separation flow and biochemical treatment are commonly used at home and abroad. The chemical separation treatment process generally comprises units of deacidification, extraction, deamination, solvent recovery and the like to remove acid gas, recover phenol, ammonia and the like. The waste water is pretreated by flash evaporation, sedimentation and the like to remove tar and partial light oil, enters a deacidification tower to remove acid gas, and then enters an extraction tower to extract and dephenolize.
The patent number ZL20110204145. X of the invention discloses an energy-saving phenol-ammonia wastewater recovery treatment process. The invention mainly uses the equipment coupling among the deacidification tower, the deamination tower and the water tower, namely, the crude ammonia condenser at the top of the deamination tower is simultaneously used as a reboiler of the deacidification tower and the water tower, the differential pressure rectification technology is utilized to realize the ladder comprehensive utilization of a heat source, the energy consumption in the phenol-ammonia wastewater treatment process is reduced, the consumption of steam and circulating water is greatly saved, and the purposes of saving energy and reducing consumption are achieved while the ammonia and phenol in coal gasification wastewater are recovered. The invention solves the technical problem of high energy consumption of phenol-ammonia wastewater recovery treatment in the traditional coal gasification process, realizes comprehensive utilization of energy, does not reduce equipment investment, saves energy, reduces consumption thoroughly, and further simplifies the process flow and the space of operation difficulty.
Patent CN102863112a,20130109 discloses a phenol-ammonia wastewater recovery method adopting a single tower to deacidify and deaminize simultaneously, which mainly adopts a side extraction and differential pressure rectification technology through a deacidification and deaminizing coupling tower to realize the process of deacidification and deaminizing simultaneously in the single tower, recovers ammonia and phenol in coal gasification wastewater, saves energy and reduces emission, simplifies the process flow, reduces equipment investment, reduces operation difficulty, realizes equipment coupling, simplifies the flow, but has larger equipment investment and low phenol recovery rate, and further integrally couples multi-tower equipment in the process, realizes deacidification, deaminize and deaminize simultaneously in the single tower, develops a high-efficiency extractant and improves the phenol recovery space.
Disclosure of Invention
In order to improve the dephenolization efficiency of coal tar hydrogenation wastewater, and particularly to heterocyclic compounds such as polyphenol, pyridine and the like in the wastewater, the invention provides an FU type composite extractant suitable for coal tar hydrogenation wastewater treatment.
Meanwhile, the invention also provides a multifunctional composite tower hydrogenation wastewater treatment device and a multifunctional composite tower hydrogenation wastewater treatment method matched with the FU type composite extractant, which can effectively separate and recycle valuable substances such as ammonia nitrogen, sulfides, oil, phenol and the like in wastewater, simplify the traditional process flow of extracting phenol by distilling ammonia, reduce equipment investment and reduce energy consumption.
The technical scheme adopted by the invention is as follows:
the FU type composite extractant suitable for the coal tar hydrogenation wastewater treatment comprises the following raw materials in percentage by mass:
further limited, the amine complexing agent is formed by compounding tri-n-octylamine and tributyl phosphate according to a mass ratio of 2:1.
Further defined, the other benzene species is in particular benzene, toluene or xylene or any mixture thereof.
The FU type composite extractant is applied to countercurrent extraction and dephenolization of deamination and deacidification wastewater in coal tar hydrogenation wastewater treatment, and the extraction rate of phenolic compounds can reach 99%.
The multifunctional composite tower hydrogenation wastewater treatment device matched with the FU type composite extractant suitable for coal tar hydrogenation wastewater treatment comprises a tower body, wherein the tower body is internally divided into a deacidification deamination section, an extraction section and a phenol recovery section from top to bottom, the deacidification deamination section, the extraction section and the phenol recovery section are separated by a baffle to form independent closed spaces, the diameter of the deacidification deamination section is smaller than that of the extraction section, and the diameter of the extraction section is smaller than that of the phenol recovery section; the ratio of the heights of the deacidification and deamination section, the extraction section and the phenol recovery section is 1:1.3-1.5:1, and the extraction section is filled with the FU type composite extractant suitable for coal tar hydrogenation wastewater treatment.
Further limited, the ratio of the tower diameters of the deacidification and deamination section, the extraction section and the phenol recovery section is 1:1.2-1.4:1.5-1.6.
Further limiting, wherein the top of the extraction section is provided with an oil phase outlet, the upper side wall of the extraction section is provided with a liquid inlet communicated with a wastewater outlet of the deamination deacidification section, and the lower side wall of the extraction section is provided with an extractant circulation inlet; a dephenolization wastewater outlet is formed in the bottom of the extraction section; the inner cavity of the extraction section is provided with a packing layer and a sieve plate layer which are distributed at intervals, the sieve plate layer is arranged above the packing layer, the interval between the packing layer and the sieve plate layer is 0.25-0.4 m, and the height ratio of the packing layer to the sieve plate layer is 1.5-2:1; the aperture of the sieve plate layer is 3-8 mm, and the distance between the upper sieve plate and the lower sieve plate of the sieve plate layer is 0.4-0.6m.
Further limiting, wherein the inner cavity of the phenol recovery section is provided with a plurality of layers of mesh plates, and an extraction steam outlet, an extract liquid inlet and a light phenol fraction outlet are formed above the plurality of layers of mesh plates on the side wall of the phenol recovery section from top to bottom; the extraction steam outlet is communicated with an extractant circulation inlet of the extraction section through a condenser; the extract liquid inlet is communicated with the oil phase outlet through a condenser; the bottom of the phenol recovery section is provided with a tar outlet, a reflux steam outlet and a steam inlet, the steam inlet is arranged above the reflux steam outlet, and the reflux steam outlet is arranged above the tar outlet.
The coal tar hydrogenation wastewater treatment method realized by the multifunctional composite tower hydrogenation wastewater treatment device comprises the following steps:
(1) Preheating coal tar hydrogenation wastewater, then carrying out deacidification and deamination treatment, carrying out heat exchange by utilizing saturated steam with the pressure of 2.5MPa under the condition that the temperature is 90-110 ℃ and the pressure is 0.1-0.15 MPa, removing sulfide and ammonia nitrogen in the wastewater in a stripping mode, controlling the bottom temperature of a deacidification and deamination section to be 110-140 ℃, the pressure to be 0.12-0.15 MPa, and the reflux ratio to be 3-4, wherein the removed acid gas is discharged from the upper part and is led out of NH from the side line 3 Concentrating by a flash evaporation device and then discharging to obtain deamination deacidification wastewater, cooling to 30-50 ℃, and entering an extraction section;
(2) In the extraction section, the deamination deacidification wastewater and the FU type composite extractant are subjected to countercurrent extraction through a stuffing layer and a sieve plate layer which are distributed in a staggered way, the phenol-oil mixture is separated from water, the extraction temperature is 30-50 ℃, the pressure is 0.1-0.15 MPa, the extracted phenol-oil mixture is discharged from the upper part and is collected into an extract buffer tank, and the dephenolization wastewater is discharged from the lower part;
(3) Heating the phenol oil mixture collected by the extract cache tank to 50-70 ℃, performing heat exchange with saturated steam of 2.5MPa under the conditions of the temperature of 50-70 ℃ and the pressure of 0.1-0.15 MPa, separating the phenol oil from the extracting agent, enabling the temperature after heat exchange to be 140-180 ℃ and the pressure to be 0.1-0.15 MPa, enabling the reflux ratio to be 0.2-0.4, cooling the extracting agent to 30-50 ℃, and returning part of the phenol oil mixture to the step (2) for circular extraction after heat exchange between a heating heat source serving as the phenol oil mixture and the phenol oil mixture, and mixing the other part of the phenol oil mixture and the phenol oil mixture collected by the extract cache tank for repeated treatment; separating light phenol, and washing with iodine to obtain crude phenol product; and cooling the tar separated from the bottom, and discharging to finish the coal tar hydrogenation wastewater treatment method.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention simplifies the coupling of four towers of an industrial deacidification deamination tower, an extraction tower, a water tower and a phenol tower into a highly integrated composite single tower to realize the functions of deacidification deamination, dephenolization and the like, and is matched with a novel FU type composite extractant and a novel composite tower technology to realize the coupling of three towers, wherein a deacidification deamination section, an extraction section and a phenol recovery section are arranged in the tower, so that low-pressure operation can be realized, the operation and the processing and the manufacturing are easy, the tradition of equipment plane arrangement is broken, the number of the required towers in the whole device is reduced, the occupied area is reduced, the processing and the manufacturing are simple, and the investment of the whole equipment is reduced by about 25 percent; in addition, according to the different treatment capacity of the process coal tar hydrogenation wastewater, the pressure and the temperature in the tower, the stable operation in the tower is ensured, the equipment structure adopts a gradually-increased variable-diameter tower structure, and the coupling degree is high.
(2) The extraction section of the invention adopts a novel composite tower which is designed independently, a sieve plate in the tower and a filler are combined, a sieve plate is arranged on the upper part, the filler is arranged under the sieve plate, an internal composite tower plate is formed, the sieve plate plays a role in liquid redistribution, the filler adopts an FU type composite extractant which is suitable for coal tar hydrogenation wastewater treatment, plays a role in gas redistribution, the gas-liquid contact on a mass transfer element is good, entrainment among traditional tower plates is eliminated, the mass transfer efficiency is very high, and the wastewater treatment amount is obviously increased. The FU novel efficient composite extractant has good performance, the entrainment of the extractant in the water phase is almost zero, the arrangement of a water tower for taking and recycling the extractant is avoided, and the extractant can efficiently remove the heterocyclic compounds such as polyhydric phenol, pyridine and the like which are difficult to be degraded in water. Therefore, the coupling of the novel composite tower plate and the novel composite extractant can realize the efficient extraction of the phenolic compounds under normal pressure, and the extraction rate can reach about 99 percent. The COD value of the raffinate after extraction is reduced to below 80mg/L, and the problems that the recovery rate of phenol is low, the loss of extractant is large, the equipment needs negative pressure operation and the subsequent biochemical treatment is heavy in load in the traditional single extraction operation are solved. The extraction section is used as the core section of the whole composite tower, and compared with the traditional extraction tower, the required height of the device is reduced by about half under the same treatment capacity.
(3) In the phenol recovery section, the extracting agent is easy to separate and regenerate, the separation of phenol and the extracting agent is realized under normal pressure, the harsh conditions of negative pressure operation and high temperature in the traditional production are avoided, the crude phenol is effectively recovered, and the concentration of the crude phenol product can reach 99.7 percent.
(4) The waste water from the bottom of the deacidification deamination tower in the single tower structure can be used as a heating source of raw material waste water, and automatically flows into the extraction tower, the extractant at the top of the phenol tower is used as a heat source of the extract of the extraction section, and automatically flows into the solvent circulation tank, so that steam is saved, cooling water is saved, equipment conveying energy is saved, the single tower is compact in pipeline arrangement, fluid flow loss is reduced, energy consumption is reduced, public material consumption (steam and electric energy) is reduced by about 15%, and operation cost is reduced by about 16%.
Drawings
FIG. 1 is a system flow chart of a coal tar hydrogenation wastewater treatment method of example 1.
In the figure: the device comprises a preheater 1, a deacidification deamination section 2, an extraction section 3, an extract buffer tank 4, a solvent circulation tank 5, a phenol recovery section condenser 6, a phenol recovery section 7, an alkaline washing device 8, a flash evaporation device 9, a first reboiler 10, a phenol recovery section second reboiler 11 and an organic acid tank 12.
Detailed Description
The technical scheme of the present invention will now be further described with reference to the accompanying drawings and examples, but the present invention is not limited to the following embodiments.
Referring to fig. 1, the multifunctional composite tower hydrogenation wastewater treatment device comprises a tower body, wherein the tower body is internally divided into a deacidification and deamination section, an extraction section and a phenol recovery section from top to bottom, the deacidification and deamination section, the extraction section and the phenol recovery section are separated by a baffle to form independent closed spaces, the height of the whole tower body is 38-45m, the diameter of the deacidification and deamination section is smaller than the diameter of the extraction section, and the diameter of the extraction section is smaller than the phenol recovery section, namely the ratio of the tower diameters is 1:1.2-1.4:1.5-1.6; the ratio of the heights of the deacidification and deamination section, the extraction section and the phenol recovery section is 1:1.3-1.5:1, and the gradually-increased reducing type tower structure is beneficial to ensuring and stably operating the treatment pressure of the wastewater in the tower.
Further, the deacidification and deamination section mainly uses saturated steam with the pressure of 2.5MPa to perform heat exchange, and removes sulfide and ammonia nitrogen in raw material wastewater in a stripping mode. The inner cavity of the deacidification and deamination section is provided with a plurality of layers of screen plates, so that the waste water and the steam are uniformly distributed through the screen plates and fully contacted, and the stripping efficiency is improved. The side wall above the screen plate is provided with a water inlet and a liquid nitrogen outlet, the side wall below the screen plate is provided with a steam reflux port, the top of the deacidification and deamination section is provided with an acid gas outlet, the middle of the deacidification and deamination section is provided with a steam inlet, the bottom of the deacidification and deacidification section is provided with a deamination and deacidification waste water outlet, and the steam inlet is arranged above the steam reflux port. During treatment, the water inlet of the deacidification deamination section is communicated with hot water of the preheater, the deamination deacidification wastewater outlet of the deacidification deamination section is communicated with the hot liquid inlet of the preheater through a pipeline, so that the treated wastewater is preheated and then subjected to deacidification deamination treatment, and the deacidification deamination wastewater can also be used as a heat source to perform heat exchange with the water inlet in the preheater, so that the preheating efficiency is improved, and the energy consumption is saved. The deacidification and deamination section is also communicated with the first reboiler through a steam inlet and a steam reflux port to form a steam cycle.
Further, the extraction section mainly removes phenol, oil and other organic matters in the wastewater. An oil phase outlet is arranged at the top of the extraction section and is communicated with an extract buffer tank through a pipeline, and the extracted phenolate oil mixture is temporarily stored in the extract buffer tank. A liquid inlet is arranged on the side wall above the extraction section and is communicated with a deacidification deamination wastewater outlet of the preheater through a pipeline. An extractant circulation inlet is formed in the side wall below the extraction section and is communicated with a solvent circulation tank through a pipeline, and the solvent circulation tank is communicated with the phenol recovery section so as to recycle the extractant. And a dephenolization waste water outlet is arranged at the bottom of the extraction section, and the dephenolization waste water which is qualified in treatment after extraction is discharged. The extraction section is a composite tower combining a packing tower and a plate tower, a packing layer and a sieve plate layer which are distributed at intervals are arranged in the extraction section, the sieve plate layer is arranged above the packing layer, the interval between the packing layer and the sieve plate layer is 0.25-0.4 m, and the height ratio of the packing layer to the sieve plate layer is as follows: 1.5-2:1. The filler of the filler layer is a commercially available regular corrugated filler, such as silk screen corrugated filler, perforated plate corrugated filler, mesh corrugated filler and the like. The sieve plate of the sieve plate layer is a common sieve plate which is made of an unlimited material and is commercially available, the aperture of the sieve plate layer is 3-8 mm, and the interval between the sieve plates of the sieve plate layer is 0.4-0.6m. The extraction section is filled with FU type composite extractant.
Further, an extraction steam outlet, an extract liquid inlet, a light phenol fraction outlet and an extract liquid reflux port are formed in the upper half side wall of the phenol recovery section from top to bottom, a tar outlet, a reflux steam outlet and a steam inlet are formed in the lower half side wall, wherein the extract liquid inlet is communicated with a heat exchange liquid outlet of a condenser through a pipeline, the extraction steam outlet is communicated with a heat steam source inlet of the condenser through a pipeline, a heat exchange liquid inlet of the condenser is communicated with an outlet of an extract buffer tank through a pipeline, a condensate outlet of the condenser is communicated with a solvent circulation tank through a pipeline, and heat exchange and preheating are carried out on a phenol-oil mixture to be fed into the phenol recovery section by taking extractant hot steam discharged by the phenol recovery section as a heat source to recover the heat source, so that the recovery efficiency of the phenol recovery section is improved. The inner cavity of the phenol recovery section is provided with a plurality of layers of mesh plates, and the separation of the phenol oil and the extractant is realized by utilizing the mass transfer and the heat transfer of the mesh plates and the steam stripping of saturated steam. The reflux steam outlet and the steam inlet are arranged below the mesh plate, and the external circulation of steam is formed through a second reboiler connected with the outside.
The solvent circulating tank is mainly used for caching and circulating recycled extractant, is respectively communicated with an extractant circulating inlet of the extraction section, an extract liquid reflux port of the phenol recovery section and a condensate liquid outlet of the condenser, and is mainly used for circulating part of the circulating extractant condensed by the condenser to be used as extractant supplementing liquid of the extraction section, and part of the circulating extractant flows back to the phenol recovery section for repeated treatment, so that the phenol recovery rate is further improved.
Peripheral devices mentioned for the above system, such as preheaters, condensers, extract buffer tanks, solvent circulation tanks, etc., belong to auxiliary plants, which are added in order to be able to recycle heat energy or to increase the treatment efficiency.
The method for treating coal tar hydrogenation wastewater by utilizing the multifunctional composite tower hydrogenation wastewater treatment device can be realized by the following steps:
(1) Preheating coal tar hydrogenation wastewater, then, entering a deacidification and deamination section for deacidification and deamination treatment, carrying out heat exchange by utilizing saturated steam with the pressure of 2.5MPa under the conditions of the temperature of 90-110 ℃ and the pressure of 0.1-0.15 MPa, removing sulfide and ammonia nitrogen in the wastewater in a stripping mode, controlling the bottom temperature of the deacidification and deamination section to be 110-140 ℃, controlling the pressure to be 0.12-0.15 MPa, and leading out NH from the side line of the removed acid gas through the upper discharge part, wherein the reflux ratio is 3-4 3 Concentrating and discharging the wastewater through a liquid nitrogen outlet into a flash evaporation device, obtaining deamination and deacidification wastewater at the bottom, performing heat exchange with coal tar hydrogenation wastewater raw materials in a preheater, cooling to 30-50 ℃, and entering an extraction section;
(2) In the extraction section, countercurrent extraction is carried out on the deamination deacidification wastewater cooled down and the FU type composite extractant, the phenol oil mixture and water are separated, the structural design of a composite tower plate is utilized to be matched with the novel FU type composite extractant, the extraction temperature is adjusted to be 30-50 ℃, the pressure is adjusted to be 0.1-0.15 MPa, the extractant can maximally exert the extraction efficiency, the extracted phenol oil mixture is discharged from the upper part and is collected to an extract buffer tank; the dephenolized wastewater reaches the standard and is discharged from the lower part;
the FU type composite extractant is suitable for treating coal tar hydrogenation wastewater, and comprises 60-80% (volume fraction) of amine complexing agent, 10-15% (volume fraction) of MIBK, 6-8% (volume fraction) of isopropyl ether and the balance of other components. The amine complexing agent is prepared by compounding tri-n-octylamine and tributyl phosphate according to the mass ratio of 2:1.
(3) Heating the phenol oil mixture collected by the extract buffer tank to 50-70 ℃, performing heat exchange with saturated steam of 2.5MPa under the conditions of the temperature of 50-70 ℃ and the pressure of 0.1-0.15 MPa to separate phenol oil from the extracting agent, keeping the bottom temperature of the phenol recovery section at 140-180 ℃ and the pressure of 0.1-0.15 MPa and the reflux ratio at 0.2-0.4, forming extracting agent hot steam after the extracting agent is subjected to heat exchange by the saturated steam, discharging the extracting agent into a condenser from the top of the phenol recovery section, performing heat exchange preheating on the phenol oil mixture to be discharged from the extract buffer tank as a heat source of the condenser, liquefying and cooling the extracting agent to 30-50 ℃, entering a solvent circulation tank for buffering, returning part of the extracting agent to the step (2) as extracting agent supplement liquid for circulating extraction, returning the other part of the extracting agent to the phenol recovery section and the phenol oil mixture for mixing and repeating treatment, and further separating a small amount of phenol contained in the extracting agent; light phenol separated from the extractant is distilled and subjected to an iodine washing device to produce a crude phenol product; and the tar separated from the bottom of the phenol recovery section is discharged as a tar product after being cooled, thus finishing the treatment of the coal tar hydrogenation wastewater.
The FU type composite extractant applicable to coal tar hydrogenation wastewater treatment can be used for countercurrent extraction dephenolization with deamination deacidification wastewater in the coal tar hydrogenation wastewater treatment, and the extraction rate of phenolic compounds can reach 99%. The multifunctional composite tower hydrogenation wastewater treatment device is special for the treatment method. Except that the composite tower plate of the extraction section and the FU composite extractant are required to be creatively designed, other chemical raw materials of the reagents (MIBK methyl isobutyl ketone, isopropyl ether and the like) are all commercially available, examples 1-3 are implementation cases adopting the technology of the invention, and comparative example 1 is the treatment effect of comparing different equipment and technological parameters.
Example 1
In this example, the ratio of the heights of the deacidification and deamination section, the extraction section and the phenol recovery section is 1:1.5:1, and the ratio of the tower diameters is 1:1.3:1.5.
Will be 8m 3 Coal tar hydrogenation wastewater of/h, the temperature is 40 ℃, the concentration is 3600mg/L, the total phenol is 14800mg/L, ammonia nitrogen is 6500mg/L, sulfide is 640mg/L, CODcr is 98000mg/L, the wastewater enters into a deacidification and deamination section 2 after being preheated to 90 ℃ in a preheater 1, the top temperature of the section is kept to be 100 ℃, the pressure is 0.12MPa, saturated steam of 2.5MPa is utilized to carry out heat exchange on the raw wastewater at the bottom of the deacidification and deamination section 2 in a first reboiler 10, the bottom temperature is controlled to be 130 ℃, the pressure is 0.12MPa, the reflux ratio is 3, sulfide and ammonia nitrogen are gasified at high temperature, the removed acid gas is removed from the raw wastewater in a stripping mode, and the removed acid gas is discharged from the top and NH 3 Through flash distillation device9, concentrating, then, removing the liquid ammonia refining device, refluxing deamination deacidification wastewater into a preheater 1, performing heat exchange with raw material wastewater, cooling to 30 ℃ after cooling, and taking the cooled deamination deacidification wastewater as the top feed of the extraction section 3. The deacidification deamination wastewater enters an extraction section 3 from the top and is subjected to countercurrent extraction on a composite column plate with an FU type composite extractant which is suitable for coal tar hydrogenation wastewater treatment and enters from the bottom of the section, wherein in the composite extraction of the embodiment, the mass fraction of an amine complexing agent (tri-n-octylamine: tributyl phosphate compound=2:1) is 80%, the mass fraction of a mixture of MIBK10%, isopropyl ether 8% and benzene and toluene (3:1) is 2%. In the embodiment, a composite tower mode is adopted, an extraction section is a composite tower formed by combining a packed tower and a plate tower, a packing layer and a sieve plate layer which are distributed at intervals are arranged in the composite tower, the sieve plate layer is arranged above the packing layer, the aperture of the sieve plate is 3mm, and the interval between the sieve plates is 0.6m; the lower layer is mesh corrugated filler, the interval between the filler layer and the sieve plate layer is 0.3m, and the height ratio of the filler layer to the sieve plate layer is 1.5:1. And the extraction section is filled with an FU type composite extractant. Separating the phenol-oil mixture from water in the extraction section, keeping the temperature at the top at 30 ℃ and the pressure at 0.12MPa, keeping the temperature at the bottom at 30 ℃ and the pressure at 0.13MPa, discharging the extracted phenol-oil mixture from the top of the extraction section 3, and collecting the extracted phenol-oil mixture into an extract buffer tank 4 as a feed of a phenol recovery section 7; and meanwhile, the dephenolized waste water obtained by extraction is discharged from the bottom for further biochemical treatment. After the phenol oil mixture collected by the extract buffer tank 4 is pressurized by a pump, the phenol oil mixture is subjected to heat exchange with the extractant hot gas at the top of the phenol recovery section 7 in the phenol recovery section condenser 6 to be heated to 70 ℃, the mixture enters the phenol recovery section 7 as the feed of the phenol recovery section 7, the temperature of the tower top of the phenol recovery section 7 is controlled to be 70 ℃, the pressure is 0.12MPa, the tower bottom liquid of the phenol recovery section 7 is subjected to heat exchange with saturated steam with the pressure of 2.5MPa in the second reboiler 11 of the phenol recovery section, the tower bottom temperature is controlled to be 160 ℃, the pressure is 0.15MPa, the reflux ratio is 0.25, the extractant is boiled, the phenol oil is separated from the extractant, the extractant steam is discharged at the top of the phenol recovery section, is cooled to 30 ℃ by the phenol recovery section condenser 6 and is liquefied, the mixture is conveyed into the solvent circulation tank 5, a part of the extractant is recycled as the extractant of the extraction section 3, and the rest part of the extractant is refluxed to the top of the phenol recovery section 7 to participate in the circulation, and the light phenol fraction separated from the phenol recovery section 7 is output after passing through the alkaline washing device 8Crude phenol product as raw material for phenol refining; and cooling and discharging tar extracted from the bottom of the phenol recovery section 7 to finish the treatment of coal tar hydrogenation wastewater. The detection results of chemical components in the wastewater treated by the deacidification and desulfurization section, the extraction section and the phenol recovery section are shown in table 1.
Example 2
In this example, the ratio of the heights of the deacidification and deamination section, the extraction section and the phenol recovery section is 1:1.4:1, and the ratio of the tower diameters is 1:1.2:1.6.
Will be 12m 3 Coal tar hydrogenation wastewater of/h, the temperature is 40 ℃, the concentration is 3800mg/L, the total phenol is 13800mg/L, the ammonia nitrogen is 7000mg/L, the sulfide is 720mg/L, CODcr is 99000mg/L, the wastewater enters into a deacidification and deamination section 2 after being preheated to 90 ℃ in a preheater 1, the top temperature of the section is kept at 90 ℃, the pressure is 0.1MPa, the saturated steam of 2.5MPa is utilized to carry out heat exchange on the wastewater at the bottom of the deacidification and deamination section 2 in a first reboiler 10, the bottom temperature is controlled at 110 ℃, the pressure is 0.15MPa, the reflux ratio is 2.5, sulfide and ammonia nitrogen are gasified at high temperature, the removed acid gas is discharged from the wastewater through the top in a stripping mode, and NH 3 Concentrating by a flash evaporation device 9, then removing liquid ammonia refining device, enabling deamination deacidification waste water to flow back to a preheater 1 to exchange heat with raw material waste water, cooling to 40 ℃ after cooling, and taking the cooled raw material waste water as the top feed of the extraction section 3. The deacidification deamination wastewater enters an extraction section 3 from the top and is subjected to countercurrent extraction on a composite column plate with an FU type composite extractant which is suitable for coal tar hydrogenation wastewater treatment and enters from the bottom of the section, wherein in the composite extraction of the embodiment, the volume fraction of an amine complexing agent (tri-n-octylamine: tributyl phosphate compound=2:1) is 75%, the MIBK is 15%, the isopropyl ether is 8%, and the benzene and the xylene are 2% of the mixture according to the ratio of 1:1. The extraction section is a composite tower combining a packing tower and a plate tower, a packing layer and a sieve plate layer which are distributed at intervals are arranged in the extraction section, the sieve plate layer is arranged above the packing layer, the aperture of the sieve plate is 4mm, and the interval between the sieve plates is 0.5m; the lower layer is mesh corrugated filler, the interval between the filler layer and the sieve plate layer is 0.4m, and the height ratio of the filler layer to the sieve plate layer is as follows: 1.8:1. And the extraction section is filled with an FU type composite extractant. Separating the phenolate oil mixture from the water in the extraction stage, maintaining the top temperature atThe pressure is 0.1MPa at 40 ℃, the bottom temperature is 40 ℃, the pressure is 0.12MPa, the phenol oil mixture obtained by extraction is discharged from the top of the extraction section 3 and is collected into an extract buffer tank 4 to be used as the feed of a phenol recovery section 7; and meanwhile, the dephenolized waste water obtained by extraction is discharged from the bottom for further biochemical treatment. After the phenol oil mixture collected by the extract buffer tank 4 is pressurized by a pump, the phenol oil mixture is subjected to heat exchange with extractant hot gas at the top of the phenol recovery section 7 in the phenol recovery section condenser 6 to be heated to 60 ℃, the mixture enters the phenol recovery section 7 as feed of the phenol recovery section 7, the temperature of the tower top of the phenol recovery section 7 is controlled to be 60 ℃, the pressure is 0.1MPa, the tower bottom liquid of the phenol recovery section 7 is subjected to heat exchange with saturated steam with the pressure of 2.5MPa in the phenol recovery section second reboiler 11, the tower bottom temperature is controlled to be 140 ℃, the pressure is 0.1MPa, the reflux ratio is 0.2, the extractant is boiled, the phenol oil is separated from the extractant, the extractant steam is discharged at the top of the phenol recovery section, is cooled to 30 ℃ by the phenol recovery section condenser 6 and is liquefied, the liquefied by the solvent circulation tank 5, a part of the extractant is recycled as the extractant of the extraction section 3, the rest part of the extractant is refluxed to the top of the phenol recovery section 7 to participate in the circulation, and the light phenol fraction separated from the phenol recovery section 7 is subjected to be produced into crude phenol products after passing through the alkaline washing device 8 as raw materials for phenol refining; and cooling and discharging tar extracted from the bottom of the phenol recovery section 7 to finish the treatment of coal tar hydrogenation wastewater. The detection results of chemical components in the wastewater treated by the deacidification and desulfurization section, the extraction section and the phenol recovery section are shown in table 1.
Example 3
In this example, the ratio of the heights of the deacidification and deamination section, the extraction section and the phenol recovery section is 1:1.3:1, and the ratio of the tower diameters is 1:1.4:1.5.
Will be 15m 3 Coal tar hydrogenation wastewater of/h, the temperature is 40 ℃, the concentration is 3800mg/L, the total phenol is 12800mg/L, the ammonia nitrogen is 7200mg/L, the sulfide is 640mg/L, the CODcr is 100000mg/L, the wastewater enters into the deacidification and deamination section 2 after being preheated to 110 ℃ in the preheater 1, the top temperature of the section is kept at 110 ℃ and the pressure is 0.15MPa, saturated steam of 2.5MPa is utilized to carry out heat exchange on the raw material wastewater at the bottom of the deacidification and deamination section 2 in the first reboiler 10, the bottom temperature is controlled to be 140 ℃, the pressure is 0.13MPa, the reflux ratio is 4, the sulfide and the ammonia nitrogen are gasified at high temperature, and the method is realized byStripping mode is adopted to remove the acid gas from the raw material wastewater, and the removed acid gas is discharged from the top and NH is discharged from the top 3 Concentrating by a flash evaporation device 9, removing liquid ammonia refining device, refluxing deamination deacidification wastewater into a preheater 1, performing heat exchange with raw material wastewater, cooling to 30 ℃ after cooling, and taking the cooled deamination deacidification wastewater as the top feed of the extraction section 3. The deacidification deamination wastewater enters an extraction section 3 from the top and is subjected to countercurrent extraction on a composite column plate with an FU type composite extractant which is suitable for treating coal tar hydrogenation wastewater and enters from the bottom of the section, wherein in the composite extraction of the embodiment, the volume fraction of an amine complexing agent (tri-n-octylamine: tributyl phosphate compound=2:1) is 60%, MIBK12%, isopropyl ether 6%, other benzene substances are 2%, and the other benzene substances are mixed by benzene, toluene and dimethylbenzene according to the mass ratio of 1:1:1. In the embodiment, a composite tower mode is adopted, an extraction section is a composite tower formed by combining a packed tower and a plate-type tower, the upper layer of the composite tower is a sieve plate, the aperture on the sieve plate is 8mm, and the interval between the sieve plates is 0.4m; the lower layer is silk screen corrugated filler, the interval between the filler layer and the sieve plate layer is 0.25m, and the ratio of the heights of the filler layer to the sieve plate layer is 2:1. And the extraction section is filled with an FU type composite extractant. Separating the phenol-oil mixture from water in the extraction section, keeping the temperature at the top of 50 ℃, the pressure at 0.15MPa, the temperature at the bottom of 50 ℃ and the pressure at 0.15MPa, discharging the extracted phenol-oil mixture from the top of the extraction section 3, and collecting the extracted phenol-oil mixture into an extract buffer tank 4 as a feed of a phenol recovery section 7; and meanwhile, the dephenolized waste water obtained by extraction is discharged from the bottom for further biochemical treatment. After the phenol oil mixture collected by the extract buffer tank 4 is pressurized by a pump, the phenol oil mixture is subjected to heat exchange with the extractant hot gas at the top of the phenol recovery section 7 in the phenol recovery section condenser 6 to be heated to 50 ℃, and enters the phenol recovery section 7 as the feed of the phenol recovery section 7, the temperature of the tower top of the phenol recovery section 7 is controlled to be 50 ℃, the pressure is 0.15MPa, the tower bottom liquid of the phenol recovery section 7 is subjected to heat exchange with saturated steam with the pressure of 2.5MPa in the second reboiler 11 of the phenol recovery section, the tower bottom temperature is controlled to be 180 ℃, the pressure is 0.14MPa, the reflux ratio is 0.4, the extractant is boiled, the phenol oil is separated from the extractant, the extractant steam is discharged at the top of the phenol recovery section, is cooled to 30 ℃ by the phenol recovery section condenser 6 and is liquefied, and is conveyed into the solvent circulation tank 5, and part of the extractant is recycled as the remainder of the extraction section 3The light phenol fraction separated from the side line of the phenol recovery section 7 is subjected to alkaline washing device 8 to produce a crude phenol product which is used as a raw material for phenol refining; and (3) extracting tar from the bottom of the phenol recovery section 7, cooling and discharging to finish the treatment of coal tar hydrogenation wastewater. The detection results of chemical components in the wastewater treated by the deacidification and desulfurization section, the extraction section and the phenol recovery section are shown in table 1.
The results of the detection of the chemical components of the wastewater treatment in each of the deacidification and desulfurization section, the extraction section and the phenol recovery section in examples 1 to 3 are shown in Table 1.
Table 1 examples 1 to 3 detection results of chemical components of wastewater treatment in each of the deacidification and desulfurization section, the extraction section, and the phenol recovery section
The wastewater treated by the coal tar hydrogenation wastewater treatment method of the invention is compared with the wastewater treated by the common deacidification deamination tower, extraction tower, water tower and phenol tower treatment process in comparative example 1, and the results are shown in the following table 2.
Table 2 shows a comparison of the wastewater sample measurements after treatment by the method of the invention and the method of comparative example 1
As can be seen from the comparison of Table 2, the total phenol removal rate of the wastewater treated by combining the multifunctional composite tower hydrogenation wastewater treatment device and the FU type composite extractant suitable for coal tar hydrogenation wastewater treatment and the wastewater treatment method is high, the phenol extraction rate is more than 99%, and the removal rate of volatile phenol and polyphenol is obviously higher than that of the conventional treatment.
The FU type composite extractant applicable to coal tar hydrogenation wastewater treatment of the invention is compared with the treatment of methyl isobutyl ketone and isopropyl ether alone, and the results are shown in the following table 3.
Table 3 shows the comparison of wastewater treatment effects under different extractants
As can be seen from Table 3, the FU type composite extractant suitable for treating coal tar hydrogenation wastewater has obviously improved treatment effect compared with the polyphenol, volatile phenol and total phenol of methyl isobutyl ketone and isopropyl ether, and has less loss of extractant and obviously reduced CODcr concentration after treatment.
In addition, the extractant of the invention also needs to be matched with the composite tower plate of the extraction section of the invention, the structural optimization and the selection of the extractant complement each other, the synergistic effect is achieved, and the structure of the composite tower plate is optimized through the following test, and the table 4 is referred to.
Table 4 shows the comparison of wastewater treatment effects of composite trays with different parameters
As can be seen from the comparison of Table 4, when the packing height of the composite column plate is 0.15m, the distance between the column plate and the packing is 0.15m, and the distance between the composite column plate and the column plate is 0.4m, the extraction efficiency is obviously higher than that of other parameters, and the phenol content in the treated wastewater and the concentration of CODcr after the treatment are obviously lower than those of the wastewater treatment effects of other parameters.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the invention in any way, but any simple modification, equivalent variation and modification made to the above embodiments according to the technical principles of the present invention shall fall within the scope of the technical solutions of the present invention.
Claims (6)
1. The coal tar hydrogenation wastewater treatment method is characterized by being realized by a multifunctional composite tower hydrogenation wastewater treatment device;
the multifunctional composite tower hydrogenation wastewater treatment device comprises a tower body, wherein the tower body is internally divided into a deacidification and deamination section, an extraction section and a phenol recovery section from top to bottom, the deacidification and deamination section, the extraction section and the phenol recovery section are separated by a baffle to form independent closed spaces, the diameter of the deacidification and deamination section is smaller than that of the extraction section, and the diameter of the extraction section is smaller than that of the phenol recovery section; the ratio of the heights of the deacidification and deamination section, the extraction section and the phenol recovery section is 1:1.3-1.5:1, and the extraction section is filled with an FU type composite extractant suitable for treating coal tar hydrogenation wastewater;
the FU type composite extractant comprises the following raw materials in parts by mass:
the coal tar hydrogenation wastewater treatment method comprises the following steps:
(1) Preheating coal tar hydrogenation wastewater, then carrying out deacidification and deamination treatment, carrying out heat exchange by utilizing saturated steam with the pressure of 2.5MPa under the conditions that the temperature is 90-110 ℃ and the pressure is 0.1-0.15 MPa, removing sulfide and ammonia nitrogen in the wastewater in a stripping mode, controlling the bottom temperature of a deacidification and deamination section to be 110-140 ℃, the pressure to be 0.12-0.15 MPa, and the reflux ratio to be 3-4, wherein the removed acid gas is discharged from the upper part and introduced into NH from a lateral line 3 Concentrating by a flash evaporation device and then discharging to obtain deamination deacidification wastewater, cooling to 30-50 ℃, and entering an extraction section;
(2) In the extraction section, the deamination deacidification wastewater and the FU type composite extractant are subjected to countercurrent extraction through a stuffing layer and a sieve plate layer which are distributed in a staggered way, the phenol-oil mixture is separated from water, the extraction temperature is 30-50 ℃, the pressure is 0.1-0.15 MPa, the extracted phenol-oil mixture is discharged from the upper part and is collected into an extract buffer tank, and the dephenolization wastewater is discharged from the lower part;
(3) Heating the mixture of the phenol oil collected by the extract buffer tank to 50-70 ℃, performing heat exchange with saturated steam of 2.5MPa under the conditions of the temperature of 50-70 ℃ and the pressure of 0.1-0.15 MPa, separating the phenol oil from the extracting agent, enabling the temperature after heat exchange to be 140-180 ℃ and the pressure to be 0.1-0.15 MPa, and enabling the reflux ratio to be 0.2-0.4, cooling the extracting agent to 30-50 ℃, and returning part of the mixture of the phenol oil serving as a heating heat source of the mixture of the phenol oil to the step (2) for circular extraction after performing heat exchange on the mixture of the phenol oil, and mixing the other part of the mixture of the phenol oil and the mixture of the phenol oil collected by the extract buffer tank for repeated treatment; separating light phenol, and washing with iodine to obtain crude phenol product; and cooling the tar separated from the bottom, and discharging to finish the coal tar hydrogenation wastewater treatment method.
2. The method for treating coal tar hydrogenation wastewater according to claim 1, wherein the amine complexing agent is formed by compounding tri-n-octylamine and tributyl phosphate according to a mass ratio of 2:1.
3. The method for treating coal tar and hydrogenation wastewater according to claim 1, wherein said other benzene substances are benzene, toluene or xylene or any mixture thereof.
4. The method for treating coal tar and hydrogenation wastewater according to claim 1, wherein the ratio of the tower diameters of the deacidification and deamination section, the extraction section and the phenol recovery section is 1:1.2-1.4:1.5-1.6.
5. The method for treating coal tar hydrogenation wastewater according to claim 1, characterized in that: the top of the extraction section is provided with an oil phase outlet, the upper side wall of the extraction section is provided with a liquid inlet communicated with a wastewater outlet of the deamination deacidification section, and the lower side wall of the extraction section is provided with an extractant circulation inlet; a dephenolization wastewater outlet is formed in the bottom of the extraction section; the inner cavity of the extraction section is provided with a packing layer and a sieve plate layer which are distributed at intervals, the sieve plate layer is arranged above the packing layer, the interval between the packing layer and the sieve plate layer is 0.25-0.4 m, and the height ratio of the packing layer to the sieve plate layer is 1.5-2:1; the aperture of the sieve plate layer is 3-8 mm, and the distance between the upper sieve plate and the lower sieve plate of the sieve plate layer is 0.4-0.6m.
6. The method for treating coal tar hydrogenation wastewater according to claim 5, characterized in that: the inner cavity of the phenol recovery section is provided with a plurality of layers of mesh plates, and an extraction steam outlet, an extract liquid inlet and a light phenol fraction outlet are formed above the plurality of layers of mesh plates on the side wall of the phenol recovery section from top to bottom; the extraction steam outlet is communicated with an extractant circulation inlet of the extraction section through a condenser; the extract liquid inlet is communicated with the oil phase outlet through a condenser; the bottom of the phenol recovery section is provided with a tar outlet, a reflux steam outlet and a steam inlet, the steam inlet is arranged above the reflux steam outlet, and the reflux steam outlet is arranged above the tar outlet.
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Citations (5)
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