CN112521253B - Carbon dioxide decomposition system and process of sodium phenolate - Google Patents
Carbon dioxide decomposition system and process of sodium phenolate Download PDFInfo
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- CN112521253B CN112521253B CN202011505439.1A CN202011505439A CN112521253B CN 112521253 B CN112521253 B CN 112521253B CN 202011505439 A CN202011505439 A CN 202011505439A CN 112521253 B CN112521253 B CN 112521253B
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- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 118
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 64
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 32
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 32
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 201
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 111
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 103
- 230000020477 pH reduction Effects 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 239000003546 flue gas Substances 0.000 claims abstract description 30
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 29
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000007789 gas Substances 0.000 claims description 34
- 230000001105 regulatory effect Effects 0.000 claims description 26
- 229940031826 phenolate Drugs 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 238000012856 packing Methods 0.000 claims description 11
- 230000005484 gravity Effects 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 230000005587 bubbling Effects 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- CCYFBESGMRJXCO-UHFFFAOYSA-M C(=O)=O.[Na+].C1(=CC=CC=C1)[O-] Chemical compound C(=O)=O.[Na+].C1(=CC=CC=C1)[O-] CCYFBESGMRJXCO-UHFFFAOYSA-M 0.000 claims 2
- 238000004821 distillation Methods 0.000 abstract description 3
- 238000004939 coking Methods 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000746 purification Methods 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 239000011269 tar Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/005—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from products, waste products or side-products of processes, not directed to the production of phenols, by conversion or working-up
- C07C37/007—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from products, waste products or side-products of processes, not directed to the production of phenols, by conversion or working-up from the tar industry
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/80—Organic bases or salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to equipment and a process of a tar distillation phenoxide decomposition unit in the coking industry, in particular to a carbon dioxide decomposition system and a process of sodium phenolate. The device comprises a decomposing tower, a crude phenol acidification tower, a sodium carbonate treatment tower and a primary decomposing and separating tank, wherein the decomposing tower is divided into an upper section, a middle section and a lower section; the flue gas pipeline is respectively connected with the middle section of the decomposing tower, the lower section of the decomposing tower, the upper section of the crude phenol acidification tower and the upper section of the sodium carbonate treatment tower, the upper section of the crude phenol acidification tower is connected with the middle section of the decomposing tower through a pipeline, and the upper section of the sodium carbonate treatment tower is connected with the middle section of the decomposing tower through a pipeline; the decomposing tower, the crude phenol acidification tower and the sodium carbonate treatment tower are respectively connected with the primary decomposing and separating tank through pipelines. Three towers are used for replacing six towers of the original process, three conveying pumps and three liquid level recording and adjusting instruments are reduced, so that a great amount of operation cost is saved, occupied area is reduced, and the phenoxide decomposition rate and intrinsic safety of the whole process are improved.
Description
Technical Field
The invention relates to equipment and a process of a tar distillation phenoxide decomposition unit in the coking industry, in particular to a carbon dioxide decomposition system and a process of sodium phenolate.
Background
The coal tar contains various organic matters, wherein phenols account for 1-2%, are valuable components, are mainly contained in three mixed fractions (phenol oil, naphthalene oil and wash oil) obtained after tar distillation, and are washed to obtain phenol sodium salt, namely, after the three mixed fractions are mixed with a 12% concentration NaOH solution, phenol in the mixed fractions reacts with alkali to generate water-soluble phenol sodium salt, and after standing, oil-water separation can be carried out on the mixed fractions with dephenolization to obtain the phenol sodium salt, and then the phenol sodium salt is decomposed through phenolate, namely, crude phenol is obtained through acidolysis.
The phenolate decomposition generally adopts a sulfuric acid method and a carbon dioxide decomposition method, wherein the sulfuric acid decomposition method is divided into batch decomposition and continuous decomposition.
The batch sulfuric acid decomposition method mainly comprises a batch decomposer; the sodium phenolate is charged into a decomposer, and sulfuric acid is slowly charged from an overhead tank, typically with about 75% sulfuric acid being injected while stirring. The heat generated by the decomposition process is removed with indirect cooling water. After the reaction, the reaction mixture is left for several hours, coarse powder produced by decomposition floats on the upper surface, and sodium sulfate sinks on the lower surface, so that the waste water containing sodium sulfate is firstly placed, and then crude phenol is discharged.
The process for continuously decomposing sodium phenolate by sulfuric acid adopts about 50% sulfuric acid, continuously mixes the clean sodium phenolate solution and sulfuric acid together by a jet mixer, and enters a sulfuric acid decomposition and separation tank after passing through a mixer and a phenolate decomposition heater, and can continuously obtain crude phenol and sodium sulfate wastewater by oil-water separation.
The sulfuric acid process belongs to the eliminating technology and adopts mainly carbon dioxide decomposing process.
The decomposition method of carbon dioxide is to decompose sodium phenolate by using flue gas or blast furnace gas and carbon dioxide components contained in flue gas, namely, sodium phenolate and carbon dioxide react in aqueous solution to produce crude phenol and sodium carbonate, when the carbon dioxide is excessive, the reaction produces sodium bicarbonate, and if sodium bicarbonate is found in the sodium carbonate solution, the decomposition is complete.
As shown in fig. 1, the basic flow of the carbon dioxide decomposition method is as follows:
the carbon dioxide-containing flue gas sent from the device is sent to a No. 1 decomposition tower (2), a No. 2 decomposition tower (3), a crude phenol acidification tower (4) and a sodium carbonate treatment tower (5) after being boosted by a flue gas fan (10) and is used for decomposing sodium phenolate in a liquid phase; the sodium phenolate in the sodium phenolate tank is pumped into a tail gas washing tower (1), the tail gas after phenolate decomposition introduced from the top is sprayed and washed from the bottom, and the tail gas is in countercurrent contact with the tail gas introduced from the bottom in a packing layer, and a small amount of phenol carried out in the tail gas when the phenolate decomposition is carried out on the flue gas is neutralized by the residual alkali in the sodium phenolate after the washing process, so that the tail gas is washed; then the sodium phenolate is sent into a No. 1 decomposition tower (2) through a sodium phenolate pump (11), the liquid level LRC-01 of a tail gas washing tower (1) is regulated by a first liquid regulating valve to stably control the flow of sodium phenolate, and phenolate is contacted with carbon dioxide gas entering from the bottom in parallel flow in the No. 1 decomposition tower (2) for bubbling mass transfer, so that chemical reaction is carried out to generate phenolic substances and sodium carbonate; the reaction product flows from the middle section of the column to the 2# decomposing column (3), where it continues to undergo a decomposition reaction with carbon dioxide blown in from the bottom of the column, and the above process is called primary decomposition.
The reaction product fully flowing out from the middle section of the No. 2 decomposing tower (3) is discharged into a primary decomposing and separating tank (7) for oil-water separation, primary decomposed phenol floats on the surface of liquid, fully flows to the other side through an internal partition plate, the separated primary decomposed phenol is sent into a crude phenol acidification tower (4) by a primary decomposed phenol pump (12), and in the tower, the primary decomposed phenol and carbon dioxide blown in from the bottom of the tower continue to undergo decomposition reaction, and the process is called secondary decomposition and is also a process of decomposing and purifying residual sodium phenolate in the crude phenol.
The reaction product is discharged from a full flow port in the middle section of the crude phenol acidification tower (4), flows into a secondary decomposition separation tank (8), separates the secondary decomposed phenol from the sodium carbonate aqueous solution, and is pressurized by a secondary decomposed phenol pump (13) and then is discharged.
The sodium carbonate aqueous solution separated by the primary decomposition separation tank (7) and the secondary decomposition separation tank (8) is fully discharged to the sodium carbonate working tank (9) together, the sodium carbonate working pump (14) is used for conveying the top of the sodium carbonate treatment tower (5) to be sprayed, the sodium carbonate aqueous solution is in countercurrent contact with the flue gas introduced from the bottom of the sodium carbonate treatment tower at a packing layer and is used for decomposing residual sodium phenolate in the sodium carbonate solution, the reacted reactant is conveyed to the sodium carbonate oil-water separation tower (6) by the sodium carbonate pump (15) to carry out oil-water separation, the full-flow crude phenol amount at the top is very small, the sodium carbonate is conveyed back to the primary decomposition separation tank (7), and pure sodium carbonate is fully conveyed to the sodium carbonate tank.
The existing carbon dioxide decomposition flow is multiple in equipment and single in function, all the equipment is conveyed by virtue of conveying pumps, each conveying pump is provided with a liquid level recording and adjusting instrument, and a liquid level adjusting valve I (16), a liquid level adjusting valve II (17), a liquid level adjusting valve III (18) and a liquid level adjusting valve IV (19) are arranged, so that the control is complicated, the occupied area is large, the operation cost is high, and many factors of optimization and integration are needed to be improved so as to save the land and the operation cost.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a carbon dioxide decomposition system and a process of sodium phenolate, which adopts a decomposition tower to finish the cleaning of tail gas and the primary decomposition of sodium phenolate, adopts an improved coarse phenolate acidification tower with filler to finish the secondary decomposition and oil-water separation of primary decomposed phenol, improves the decomposition rate of phenolate, adopts an improved sodium carbonate treatment tower to treat the purification and oil-water separation of sodium carbonate, uses three towers to replace six towers of the original process, reduces three conveying pumps and three liquid level recording and regulating instruments, thereby saving a large amount of operation cost, reducing occupied land and improving the decomposition rate and the intrinsic safety of phenolate of the whole process.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the carbon dioxide decomposition system of sodium phenolate comprises a decomposition tower, a crude phenol acidification tower, a sodium carbonate treatment tower and a primary decomposition separation tank, wherein the decomposition tower is divided into an upper section, a middle section and a lower section, the crude phenol acidification tower is divided into an upper section and a lower section, and the sodium carbonate treatment tower is divided into an upper section and a lower section; the flue gas pipeline is respectively connected with the middle section of the decomposition tower, the lower section of the decomposition tower, the upper section of the crude phenol acidification tower and the upper section of the sodium carbonate treatment tower through branch pipelines thereof, the upper section of the crude phenol acidification tower is connected with the middle section of the decomposition tower through pipelines, and the upper section of the sodium carbonate treatment tower is connected with the middle section of the decomposition tower through pipelines; the decomposing tower, the crude phenol acidification tower and the sodium carbonate treatment tower are respectively connected with the primary decomposing and separating tank through pipelines. And a flue gas fan is arranged on the flue gas pipeline.
The primary decomposition separation tank is provided with a sodium carbonate working pump and a pressure regulating valve on a pipeline connected with the sodium carbonate treatment tower, and a primary decomposition phenol pump and a liquid level regulating valve are arranged on a pipeline connected with the primary decomposition separation tank and the crude phenol acidification tower.
The decomposing tower is divided into an upper section, a middle section and a lower section, the top is a tail gas washing section, the middle section is a No. 1 decomposing section, the bottom is a No. 2 decomposing section, the crude phenol acidifying tower is divided into an upper section and a lower section, the upper section is a crude phenol acidifying section, a filler is arranged in the upper section, and the lower section is an oil-water separating section.
The sodium carbonate treatment tower is divided into an upper section and a lower section, wherein the upper section is a sodium carbonate treatment section, and the lower section is an oil-water separation section.
The carbon dioxide decomposition process of sodium phenolate specifically comprises the following steps:
1) The carbon dioxide-containing flue gas is sent into the middle section and the lower section of the decomposing tower, the upper section of the crude phenol acidification tower and the upper section of the sodium carbonate treatment tower after being boosted by a flue gas fan,
2) Primary decomposition:
the clean sodium phenolate is sent into the decomposing tower from the upper section of the decomposing tower, the middle section and the lower section of the decomposing tower, which are introduced from the top, are sprayed and washed from the bottom, and the tail gas after phenolate decomposition of the crude phenolate acidification tower and the sodium carbonate treatment tower is in countercurrent contact with the tail gas introduced from the bottom in a packing layer, and a small amount of phenol carried out in the tail gas when the flue gas is subjected to phenolate decomposition is neutralized by utilizing alkali remained in the cleaning procedure of the clean sodium phenolate, so that dephenolization washing effect is realized on the tail gas;
then, the sodium phenolate is automatically fed into the bottom of the middle section of the decomposition tower by self gravity, and contacts with carbon dioxide gas entering from the bottom in parallel flow in the tower for bubbling mass transfer, so that chemical reaction is carried out to generate phenolic substances and sodium carbonate;
the reaction product fully flows from the upper part of the middle section of the tower to the bottom of the lower section of the decomposing tower, and continuously carries out decomposition reaction with carbon dioxide blown in from the bottom of the tower;
3) And (3) secondary decomposition:
discharging reaction products fully flowing out from the upper part of the lower section of the decomposing tower into a primary decomposing and separating tank for oil-water separation, spraying the separated primary decomposed phenol downwards from the top of the upper section of the crude phenol acidification tower by a primary decomposed phenol pump, controlling the spraying amount by a liquid level regulating valve, and carrying out countercurrent contact with tail gas introduced from the bottom in a packing layer to continuously carry out decomposition reaction;
4) The reaction product is automatically fed into the bottom of the lower oil-water separator from the bottom of the upper section of the tower by self gravity, the secondary decomposed phenol and the sodium carbonate aqueous solution are separated, the secondary decomposed phenol is purified crude phenol, the purified crude phenol is fully fed into a crude phenol tank, and a small amount of liquid sodium carbonate aqueous solution is fed back into the primary decomposed separating tank for oil-water separation again;
5) Oil-water separation:
the sodium carbonate aqueous solution separated by the primary decomposition separation tank is sprayed from the top of the upper section of the sodium carbonate treatment tower by pumping sodium carbonate, the stability of the oil-water interface is controlled by a pressure regulating valve, the sprayed liquid is in countercurrent contact with the flue gas introduced from the bottom in a packing layer for decomposing residual sodium phenolate in the sodium carbonate solution, the reacted reactant automatically flows into the sodium carbonate oil-water separator at the lower section by self gravity for oil-water separation, the crude phenol amount fully flowing from the top is returned to the crude phenol side of the primary decomposition separation tank, and the purified sodium carbonate fully flows into the sodium carbonate tank.
Compared with the prior art, the invention has the beneficial effects that:
1) The three towers replace six towers of the original flow, three conveying pumps and three liquid level recording and adjusting instruments are reduced, so that a great amount of operation cost is saved, occupied area is reduced, and the intrinsic safety of the whole process is improved.
2) The improved crude phenol acidification tower is divided into an upper section and a lower section, wherein the upper section is a crude phenol acidification section, and the original bubbling reaction is changed into filler washing, so that the secondary decomposition rate of primary decomposed phenol can be improved in principle, and the quality of crude phenol is improved.
Drawings
Fig. 1 is a schematic and technological schematic diagram of the original system.
Fig. 2 is a schematic structural and process diagram of the present invention.
In the figure: 1-tail gas washing tower 2-1# decomposing tower 3-2# decomposing tower 4-crude phenol acidification tower 5-sodium carbonate treatment tower 6-sodium carbonate oil water separation tower 7-primary decomposing separation tank 8-secondary decomposing separation tank 9-sodium carbonate working tank 10-flue gas fan 11-sodium phenolate pump 12-primary decomposing phenol pump 13-secondary decomposing phenol pump 14-sodium carbonate working pump 15-sodium carbonate pump 16-liquid level regulating valve one 17-liquid level regulating valve two 18-liquid level regulating valve three 19-liquid level regulating valve four 20-decomposing tower 21-pressure regulating valve 22-liquid level regulating valve LRC-liquid level recording regulating instrument PRC-pressure recording regulating instrument
Detailed Description
The following is a further description of embodiments of the invention, taken in conjunction with the accompanying drawings:
as shown in fig. 2, the carbon dioxide decomposition system of sodium phenolate comprises a decomposition tower 20, a crude phenolization tower 4, a sodium carbonate treatment tower 5 and a primary decomposition separation tank 7.
A decomposing tower 20 is adopted to finish the cleaning of tail gas and the primary decomposition of sodium phenolate, the decomposing tower 20 is divided into an upper section, a middle section and a lower section, the top is a tail gas washing section, the middle section is a No. 1 decomposing section, and the bottom is a No. 2 decomposing section.
The improved crude phenol acidification tower 4 with the filler is adopted to complete secondary decomposition and oil-water separation of primary decomposed phenol, the improved crude phenol acidification tower 4 is divided into an upper section and a lower section, the upper section is a crude phenol acidification section, the original bubbling reaction is changed into filler washing, and the lower section is an oil-water separation section.
The improved sodium carbonate treatment tower 5 is adopted to treat the purification and oil-water separation of sodium carbonate, the improved sodium carbonate treatment tower 5 is divided into an upper section and a lower section, the upper section is a sodium carbonate treatment section, and the lower section is an oil-water separation section.
The flue gas pipeline is provided with a flue gas fan 10, the flue gas pipeline is respectively connected with the middle section of the decomposing tower 20, the lower section of the decomposing tower 20, the upper section of the crude phenol acidification tower 4 and the upper section of the sodium carbonate treatment tower 5 through branch pipelines thereof,
the upper section of the crude phenol acidification tower 4 is connected with the middle section of the decomposition tower 20 through a pipeline, and the upper section of the sodium carbonate treatment tower 5 is connected with the middle section of the decomposition tower 20 through a pipeline. The middle section of the decomposing tower 20 is connected with the primary decomposing and separating tank 7 through a pipeline, the lower section of the crude phenol acidification tower 4 is connected with the primary decomposing and separating tank 7 through a pipeline, and the lower section of the sodium carbonate treatment tower 5 is connected with the primary decomposing and separating tank 7 through a pipeline. The pipeline of the primary decomposition separating tank 7 connected with the sodium carbonate treatment tower 5 is provided with a sodium carbonate working pump 14 and a pressure regulating valve 21, and the pipeline of the primary decomposition separating tank 7 connected with the crude phenol acidification tower 4 is provided with a primary decomposition phenol pump 12 and a liquid level regulating valve 22.
The carbon dioxide decomposition process of sodium phenolate specifically comprises the following steps:
1) The carbon dioxide-containing flue gas sent from the flue gas pipeline is sent to the middle section and the lower section of the decomposition tower 20, the upper section of the crude phenol acidification tower 4 and the upper section of the sodium carbonate treatment tower 5 after being boosted by the flue gas fan 10, and is used for decomposing sodium phenolate in the liquid phase.
2) The clean sodium phenolate in the clean sodium phenolate tank is pumped into the upper section of the decomposition tower 20, the middle section and the lower section which are introduced from the top, the crude phenolation tower 4 and the sodium carbonate treatment tower 5 are sprayed and washed from the bottom, and the tail gas is in countercurrent contact with the tail gas introduced from the bottom in a packing layer, so that the residual alkali in the clean sodium phenolate washing procedure is utilized to neutralize a small amount of phenol carried out in the tail gas when the flue gas is subjected to phenolate decomposition, and the dephenolizing and washing effects are realized on the tail gas.
Then the sodium phenolate is automatically fed into the bottom of the middle section of the decomposition tower 20 by self gravity, and contacts with carbon dioxide gas entering from the bottom in parallel flow in the tower for bubbling mass transfer, and chemical reaction is carried out to generate phenolic substances and sodium carbonate; the reaction product flows from the upper part of the middle section of the column to the bottom part of the lower section of the decomposing column 20, where it continues to undergo decomposition reaction with carbon dioxide blown in from the bottom of the column, and the above process is called primary decomposition.
3) The reaction product fully flowing out from the upper part of the lower section of the tower is discharged into a primary decomposition separating tank 7 for oil-water separation, primary decomposed phenol floats on the surface of liquid and fully flows to the other side through an internal partition plate, the separated primary decomposed phenol is sent into the top of the upper section of the crude phenol acidification tower 4 by a primary decomposed phenol pump 12 to be sprayed downwards, the liquid level of LRC-01 is kept constant through a liquid level regulating valve 22 to control the spraying amount, and the reaction product is in countercurrent contact with tail gas introduced from the bottom in a packing layer for continuous decomposition reaction, and the process is called secondary decomposition and is also the decomposition and purification process of residual sodium phenolate in the crude phenol;
4) The reaction product is automatically fed into the bottom of the lower oil-water separator from the bottom of the upper section of the tower by self gravity, the secondary decomposed phenol and the sodium carbonate aqueous solution are separated, the secondary decomposed phenol is purified crude phenol, the purified crude phenol is fully fed into a crude phenol tank, and a small amount of liquid sodium carbonate aqueous solution is fed back into the primary decomposition separation tank 7 for oil-water separation again.
In order to ensure that the crude phenol quality of the oil-water separator at the lower section of the crude phenol acidification tower 4 is absolutely qualified, and the sodium carbonate content is small, the full flow of sodium carbonate possibly contains a small amount of crude phenol, so that the crude phenol returns to the primary decomposition separation tank 7 to carry out oil-water separation operation again.
5) The sodium carbonate aqueous solution separated by the primary decomposition separation tank 7 is sprayed by the top of the upper section of the sodium carbonate treatment tower 5 fed by the sodium carbonate working pump 14, the pipeline pressure PRC-01 before the sodium carbonate working pump 14 is controlled by the pressure regulating valve 21 to control the stability of the oil-water interface, the sprayed liquid is in countercurrent contact with the flue gas introduced from the bottom in a packing layer for decomposing the residual sodium phenolate in the sodium carbonate solution, the reacted reactant automatically flows into the sodium carbonate oil-water separator of the lower section by self gravity to carry out oil-water separation, the crude phenol amount fully flowing at the top is very small, the crude phenol is fed back to the crude phenol side of the primary decomposition separation tank 7, and the purified sodium carbonate fully flows into the sodium carbonate tank.
In order to ensure that the sodium carbonate of the oil-water separator at the lower section of the sodium carbonate treatment tower 5 contains as little phenol as possible and the crude phenol is less, the full flow of the crude phenol possibly contains a small amount of sodium carbonate, so the sodium carbonate returns to the crude phenol side of the primary decomposition separation tank 7 and is mixed with the primary decomposed phenol again to remove the crude phenol from the acidification tower for secondary decomposition.
The sodium carbonate extraction amount of the primary decomposition separation tank 7 is regulated by regulating the pressure of the extraction pipeline, so that the separation interface of the oil water is stable, and the extraction quality of sodium carbonate is further stabilized.
The invention adopts a decomposing tower 20 to finish the cleaning of tail gas and the primary decomposition of sodium phenolate, adopts an improved crude phenolate acidification tower 4 with filler to finish the secondary decomposition of primary decomposed phenol and oil-water separation, improves the decomposition rate of phenolate, adopts an improved sodium carbonate treatment tower 5 to treat the purification and oil-water separation of sodium carbonate, replaces six towers of the original flow with three towers, reduces three conveying pumps and three liquid level recording and regulating instruments, thereby saving a large amount of operation cost, reducing occupied land and improving the decomposition rate and the intrinsic safety of phenolate of the whole process.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (4)
1. The carbon dioxide decomposition system of sodium phenolate is characterized by comprising a decomposition tower, a crude phenol acidification tower, a sodium carbonate treatment tower and a primary decomposition separation tank, wherein the decomposition tower is divided into an upper section, a middle section and a lower section, the crude phenol acidification tower is divided into an upper section and a lower section, and the sodium carbonate treatment tower is divided into an upper section and a lower section;
the flue gas pipeline is respectively connected with the middle section of the decomposition tower, the lower section of the decomposition tower, the upper section of the crude phenol acidification tower and the upper section of the sodium carbonate treatment tower through branch pipelines thereof, the upper section of the crude phenol acidification tower is connected with the middle section of the decomposition tower through pipelines, and the upper section of the sodium carbonate treatment tower is connected with the middle section of the decomposition tower through pipelines; the decomposing tower, the crude phenol acidification tower and the sodium carbonate treatment tower are respectively connected with the primary decomposing and separating tank through pipelines;
the decomposing tower is divided into an upper section, a middle section and a lower section, the top is a tail gas washing section, the middle is a 1# decomposing section, and the bottom is a 2# decomposing section;
the crude phenol acidification tower is divided into an upper section and a lower section, wherein the upper section is a crude phenol acidification section, a filler is arranged in the crude phenol acidification tower, and the lower section is an oil-water separation section;
the sodium carbonate treatment tower is divided into an upper section and a lower section, wherein the upper section is a sodium carbonate treatment section, and the lower section is an oil-water separation section.
2. The sodium phenolate carbon dioxide decomposition system of claim 1, wherein the flue gas duct is provided with a flue gas fan.
3. The sodium phenolate carbon dioxide decomposition system of claim 1, wherein the primary decomposition separation tank and sodium carbonate treatment tower are provided with a sodium carbonate working pump and a pressure regulating valve on a pipeline, and the primary decomposition separation tank and crude phenolization tower are provided with a primary decomposition phenol pump and a liquid level regulating valve on a pipeline.
4. A process based on the carbon dioxide decomposition system of sodium phenolate as claimed in claim 1 or 2 or 3, characterized by comprising in particular the following steps:
1) The carbon dioxide-containing flue gas is sent to the middle section and the lower section of the decomposing tower, the upper section of the crude phenol acidification tower and the upper section of the sodium carbonate treatment tower after being boosted by a flue gas fan;
2) Primary decomposition:
the clean sodium phenolate is sent into the decomposing tower from the upper section of the decomposing tower, the middle section and the lower section of the decomposing tower, which are introduced from the top, are sprayed and washed from the bottom, and the tail gas after phenolate decomposition of the crude phenolate acidification tower and the sodium carbonate treatment tower is in countercurrent contact with the tail gas introduced from the bottom in a packing layer, and a small amount of phenol carried out in the tail gas when the flue gas is subjected to phenolate decomposition is neutralized by utilizing alkali remained in the cleaning procedure of the clean sodium phenolate, so that dephenolization washing effect is realized on the tail gas;
then the sodium phenolate is automatically fed into the bottom of the middle section of the decomposition tower by self gravity and contacts with carbon dioxide gas entering from the bottom in parallel flow in the tower for bubbling mass transfer, so as to generate phenolic substances and sodium carbonate;
the reaction product fully flows from the upper part of the middle section of the tower to the bottom of the lower section of the decomposing tower, and continuously carries out decomposition reaction with carbon dioxide blown in from the bottom of the tower;
3) And (3) secondary decomposition:
discharging reaction products fully flowing out from the upper part of the lower section of the decomposing tower into a primary decomposing and separating tank for oil-water separation, spraying the separated primary decomposed phenol downwards from the top of the upper section of the crude phenol acidification tower by a primary decomposed phenol pump, controlling the spraying amount by a liquid level regulating valve, and carrying out countercurrent contact with tail gas introduced from the bottom in a packing layer to continuously carry out decomposition reaction;
4) The reaction product is automatically fed into the bottom of the lower oil-water separator from the bottom of the upper section of the tower by self gravity, the secondary decomposed phenol and the sodium carbonate aqueous solution are separated, the secondary decomposed phenol is purified crude phenol, the purified crude phenol is fully fed into a crude phenol tank, and a small amount of liquid sodium carbonate aqueous solution is fed back into the primary decomposed separating tank for oil-water separation again;
5) Oil-water separation:
the sodium carbonate aqueous solution separated by the primary decomposition separation tank is sprayed from the top of the upper section of the sodium carbonate treatment tower by pumping sodium carbonate, the stability of the oil-water interface is controlled by a pressure regulating valve, the sprayed liquid is in countercurrent contact with the flue gas introduced from the bottom in a packing layer for decomposing residual sodium phenolate in the sodium carbonate solution, the reacted reactant automatically flows into the sodium carbonate oil-water separator at the lower section by self gravity for oil-water separation, the crude phenol amount fully flowing from the top is returned to the crude phenol side of the primary decomposition separation tank, and the purified sodium carbonate fully flows into the sodium carbonate tank.
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