CN109651092B - Clean production method and device for gas circulation coking crude phenol - Google Patents
Clean production method and device for gas circulation coking crude phenol Download PDFInfo
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- CN109651092B CN109651092B CN201910067528.3A CN201910067528A CN109651092B CN 109651092 B CN109651092 B CN 109651092B CN 201910067528 A CN201910067528 A CN 201910067528A CN 109651092 B CN109651092 B CN 109651092B
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 238000004939 coking Methods 0.000 title claims abstract description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 228
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 114
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 114
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 112
- 230000020477 pH reduction Effects 0.000 claims abstract description 92
- 239000000243 solution Substances 0.000 claims abstract description 63
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 56
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims abstract description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000011734 sodium Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000011280 coal tar Substances 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 45
- 239000000945 filler Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011269 tar Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 230000005587 bubbling Effects 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 230000005484 gravity Effects 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 239000011344 liquid material Substances 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 239000007789 gas Substances 0.000 description 72
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 21
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 239000003546 flue gas Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 230000001502 supplementing effect Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/005—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
-
- 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
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
- C07C37/66—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring by conversion of hydroxy groups to O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/86—Purification; separation; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
- C07C39/04—Phenol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/235—Metal derivatives of a hydroxy group bound to a six-membered aromatic ring
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A clean production method and a device for coking crude phenol by gas circulation aim at saving energy, protecting environment and reducing equipment corrosion; the method comprises the steps of distilling coal tar to obtain a phenol oil fraction, and washing and dephenolizing the phenol oil fraction with an NaOH aqueous solution to generate a phenol sodium salt solution; sending to the upper part of the decomposing tower to flow from top to bottom, reversely contacting with the circulating gas, and leading most of sodium phenolate to be CO 2 After the crude phenol and sodium carbonate are decomposed, the crude phenol and sodium carbonate flow into the bottom of the decomposing tower; standing and separating for 6-8 hours to finish the crude phenol and Na 2 CO 3 Separating solution, allowing the separated crude phenol to flow into a primary crude phenol middle tank, delivering to the upper part of an acidification tower, allowing the crude phenol to flow from top to bottom, contacting with circulating gas reversely, and allowing sodium phenolate to be converted into CO 2 Further decomposing and then flowing into the bottom of the acidification tower; unreacted CO 2 The gas escapes from the top of the decomposing tower and the acidification tower, enters a carbon dioxide balance tank, and is respectively conveyed to the bottoms of the decomposing tower and the acidification tower by a circulating fan for recycling, so that a gas circulating system for decomposing carbon dioxide is established.
Description
Technical Field
The invention belongs to the technical field of deep processing of high-temperature coal tar and medium-low temperature coal tar, and particularly relates to a clean production method and device for gas circulation coking crude phenol.
Background
The method for extracting phenolic substances from high-temperature coal tar and medium-low-temperature coal tar in industry comprises the steps of firstly distilling the coal tar to obtain a phenol oil fraction with relatively high phenol content. The phenol is separated by washing the fraction with aqueous NaOH solution, the principle being that NaOH reacts with the phenol to form a phenol sodium salt solution (this process is also called washing). Then the crude phenol is prepared by decomposing the sodium phenolate with an acidic substance (the process is also called fractionationSolution process). At present, the crude phenol is mainly produced by decomposing sodium phenolate in China by adopting flue gas (the effective component is CO 2 ) Two methods of decomposition and sulfuric acid decomposition, the Shandong Texas gold energy technology Co., ltd., patent CN102206140A publishes that sulfur dioxide (SO) 2 ) The decomposition of gases is also reported in the literature to use pure CO 2 The decomposition methods have certain disadvantages. Flue gas decomposition is the utilization of CO in flue gas 2 Reaction with sodium phenolate to give crude phenol and sodium carbonate (Na 2 CO 3 ) Due to the small amount of SO contained in the flue gas 2 The gas (50 mg/Nm 3-200 mg/Nm 3) and a certain amount of water generate sulfurous acid in the decomposition process, which not only corrodes the equipment, but also causes Na after decomposition 2 CO 3 The aqueous solution also contains Na 2 SO 3 And the like are not beneficial to Na 2 CO 3 Is recycled. In addition flue gas CO 2 Is very low in its CO content, depending on the source of the flue gas 2 The content is generally 10% -20% and the reaction efficiency is very low, and about 80% -90% of decomposed gas is discharged from the system to the atmosphere, so that the environment is seriously affected. By sulfur dioxide (SO) 2 ) When the gas is decomposed, sulfurous acid is generated due to the existence of water, equipment is severely corroded, and unreacted sulfur dioxide (SO 2 ) The release to the atmosphere has an environmental impact. With pure CO employed by individual enterprises 2 Decomposition due to CO 2 High concentrations can cause local CO 2 Excessive formation of sodium bicarbonate (NaHCO) 3 ) Sodium bicarbonate (NaHCO) 3 ) And the equipment is easy to be blocked by crystallization. The sulfuric acid decomposition method has a large amount of sodium sulfate (Na 2 SO 4 ) Waste liquid is produced, sodium sulfate (Na 2 SO 4 ) The waste liquid contains a lot of harmful substances, and the current wastewater treatment technology cannot treat the waste liquid well.
The main chemical reaction equations of the washing process and the decomposition process are as follows:
C 6 H 5 OH + NaOH → C 6 H 5 ONa + H 2 O
SO 2 + H 2 O→H 2 SO 3
2C 6 H 5 ONa + CO 2 + H 2 O → 2C 6 H 5 OH + Na 2 CO 3
2C 6 H 5 ONa + SO 2 + H 2 O → 2C 6 H 5 OH +Na 2 SO 3
2C 6 H 5 ONa + H 2 SO 4 → 2C 6 H 5 OH + Na 2 SO 4
small amounts of sodium bicarbonate (NaHCO) are also formed upon decomposition of the carbon dioxide 3 ）， NaHCO 3 The instability heats it above 90 ℃ to convert it entirely to sodium carbonate.
The sulfuric acid process has two processes of continuous decomposition and intermittent decomposition, no matter which process is adopted, sulfuric acid and phenol sodium salt are mixed and the decomposition temperature is controlled to be about 90 ℃, the phenol content of the phenol sodium salt is between 20% and 40%, and when sulfuric acid is added for decomposition, sulfuric acid which does not react yet exists in a dilute sulfuric acid form locally, so that the equipment is severely corroded under the condition. At present, the sodium sulfate waste liquid generated by decomposing sodium phenolate by a sulfuric acid method is difficult to treat by the sewage treatment technology in China, when sewage is treated by a biological method, if the sodium sulfate content exceeds the standard, a large amount of activated sludge is killed, and when serious, the system cannot normally operate. When the sulfuric acid is used for decomposing the sodium phenolate in the batch process, a large amount of acid mist is generated during the sulfuric acid decomposition operation because the decomposition process is an exothermic reaction, and the operation environment is seriously influenced. Although the technical literature discloses solutions to the above problems of persulfuric acid decomposition, such as "acid mist" generated when the decomposition is washed with a phenol sodium salt; for Na 2 SO 4 Performing crystallization treatment on the waste liquid; the problems of equipment corrosion and environmental pollution caused by three wastes cannot be fundamentally solved. Sulfur dioxide decomposition, with SO as disclosed in the introduction and patent application publication No. CN102206140A 2 A method for decomposing sodium phenolate and co-producing sodium sulfite. Although this method solves the problem of waste liquid discharge, there is still equipment corrosion, unreacted SO 2 The problem of influencing the operating environment is that only few enterprises are currently in use.By pure CO 2 Upon decomposition due to CO 2 High concentration, can lead to local CO in the decomposing equipment (decomposing tower and acidifying tower) 2 Excess of CO 2 Excess sodium bicarbonate (NaHCO) 3 ) Generated sodium bicarbonate (NaHCO) 3 ) The solubility in water is low, and the device is blocked by the generation of crystals, which affects the operation period. The decomposition of sodium phenolate is an important link for extracting phenolic products from coal tar, and the problems of equipment corrosion, short production period and environmental influence of waste gas are generally existed in view of several methods adopted at present in China. Therefore, it is necessary to develop a novel production process for refining, separating and extracting crude phenol from coal tar to solve the problem of equipment corrosion in the process of decomposing phenol sodium salt and the influence on the environment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a clean production method and a device for gas circulation coking crude phenol in the processing and refining process of high-temperature coal tar and medium-low-temperature coal tar, which are convenient to operate, energy-saving and environment-friendly, can reduce equipment corrosion and prolong the operation period.
The method of the invention establishes a gas circulation system by using CO with the concentration of more than 95 percent 2 The concentration of the circulating gas is regulated, and the circulating gas and the sodium phenolate are reversely contacted in a decomposition tower to carry out primary decomposition; the primary decomposition product contains a part of non-decomposed sodium phenolate, and the sodium phenolate is sent into an acidification tower to be in reverse contact with circulating gas for further decomposition to obtain a crude phenol finished product and Na 2 CO 3 Solution, na is added again 2 CO 3 And (5) recycling the solution.
The clean production method of the gas circulation coking crude phenol comprises the following steps:
(1) Distilling high-temperature coal tar or medium-low-temperature coal tar to obtain a phenol oil fraction with the phenol content of 6-20%, washing the phenol oil fraction in a vertical washing tower by using an NaOH aqueous solution, and carrying out countercurrent flowing contact on the NaOH aqueous solution and the phenol oil fraction, wherein the two substances are mutually insoluble and have specific gravity difference, and the phenol substances react with NaOH to generate a phenol sodium salt solution;
C 6 H 5 OH + NaOH → C 6 H 5 ONa + H 2 O
(2) Delivering sodium phenolate solution with temperature of 60-80deg.C and concentration of 20-40% to the upper part of decomposition tower with two layers of filler, flowing from top to bottom through the filler layer, and mixing with CO as effective component 2 Is reversely contacted with the recycle gas of CO 2 The concentration is controlled between 15% and 20%, and most of the sodium phenolate is controlled by CO in the circulating gas 2 To generate crude phenol and sodium carbonate (Na) 2 CO 3 ) Then flows into the bottom of the decomposing tower;
the phenolic product (crude phenol) can be obtained by decomposing the sodium phenolate salt. The phenol sodium salt is a strong alkali weak acid salt, and any acid with stronger acidity than phenol can decompose the phenol sodium salt, so that a phenol product is obtained.
(3) According to crude phenol and sodium carbonate (Na 2 CO 3 ) The specific gravity difference of the solution is still separated for 6 to 8 hours to finish the crude phenol and Na 2 CO 3 Separation of the solution, separated Na 2 CO 3 The solution flows to a storage tank automatically, and the crude phenol flows to a primary crude phenol middle tank automatically;
the reaction principle is as follows:
2C 6 H 5 ONa + CO 2 + H 2 O → 2C 6 H 5 OH + Na 2 CO 3
after primary decomposition of sodium phenolate, most of sodium phenolate and CO 2 The reaction produced crude phenol and an aqueous sodium carbonate solution.
(4) The crude phenol obtained by one-time decomposition and static separation also contains a part of unreacted phenol sodium salt, and is conveyed to the upper part of an acidification tower with two layers of fillers by an acidification tower raw material pump under the pressure of not lower than 0.4MPa, flows from top to bottom through a filler layer, and is mixed with circulating gas (active ingredient CO) from the bottom of the tower 2 ) Reverse contact, wherein the sodium phenolate is replaced by CO in the recycle gas 2 Further decomposing and then flowing into the bottom of the acidification tower; in order to make the acidification reaction more thorough, an acidification bubbler with an injection hole is arranged at the bottom of the acidification tower and is used for preparing CO with concentration of more than 95 percent 2 Further bubbling acidification of the acidified bottom liquid material and control of CO in the acidified bottom gas 2 The concentration is 20% -25%. The material after acid bubbling is treated under the condition of 90-95 ℃ according to the crude phenol and sodium carbonate (Na 2 CO 3 ) Static separation of specific gravity difference for 8-10 hr to obtain crude phenol and Na 2 CO 3 Separation of the solution, separated Na 2 CO 3 The solution automatically flows to a storage tank, and crude phenol meets the quality requirement and leaves the factory;
after the phenol sodium salt is decomposed for the second time, 99 percent of the phenol sodium salt is decomposed, and the non-decomposed phenol sodium salt is left in the sodium carbonate solution for further recycling or treatment, so that the crude phenol reaches the quality requirement and is sold in factories.
(5) Unreacted CO 2 The gas escapes from the top of the decomposing tower and the acidification tower, enters the carbon dioxide balance tank, and is respectively conveyed to the bottoms of the decomposing tower and the acidification tower by the circulating fan for recycling, so that a gas circulating system for decomposing carbon dioxide is established.
The carbon dioxide decomposing system realizes gas closed cycle, the sodium phenolate decomposing process is carried out in a decomposing tower and an acidifying tower, sodium phenolate solution enters the tower from the top of the tower and rises with the gas (the gas is air and CO) 2 Mixtures, CO 2 The concentration is about 15% -25%) and the sodium phenolate and part of CO are reversely contacted 2 The reaction completes the decomposition process.
To maintain system CO 2 Can supplement CO with concentration more than 95% at the outlet of the circulating fan and the acidification bubbler at the bottom of the acidification tower 2 And (3) gas.
The invention relates to a clean production device for gas circulation coking crude phenol, which comprises a decomposition tower, an acidification tower, a primary crude phenol middle tank, an acidification tower raw material pump, a sodium carbonate solution middle tank, a sodium carbonate solution pump, a carbon dioxide balance tank, an acidification bubbler and a circulating fan, wherein the decomposition tower is connected with the acidification tower through a pipeline; the decomposing tower and the acidification tower are all ring packed towers; the decomposing tower is arranged on the ground, a top gas pipeline of the decomposing tower is connected with a top gas pipeline of the acidifying tower, a bottom gas pipeline of the decomposing tower is connected with a bottom gas pipeline of the acidifying tower, a bottom primary crude phenol pipeline is connected with a feeding pipeline at the upper part of a primary crude phenol middle tank, and a bottom sodium carbonate solution pipeline is connected with a feeding pipeline at the upper part of a sodium carbonate solution middle tank; the acidification tower is arranged on the ground, a crude phenol pipeline at the bottom of the acidification tower is connected with a finished crude phenol pipeline, and a sodium carbonate pipeline at the bottom of the acidification tower is connected with a feeding pipeline at the upper part of a sodium carbonate solution middle tank; the primary crude phenol middle tank is arranged on the ground, the upper feeding pipeline is connected with the primary crude phenol pipeline at the lower part of the decomposing tower, and the lower outlet pipeline is connected with the raw material pump inlet pipeline of the acidifying tower; the acidification tower raw material pump is arranged on the ground, an inlet pipeline of the acidification tower raw material pump is connected with an outlet pipeline at the lower part of the primary crude phenol middle tank, and the outlet pipeline is connected with a feeding pipeline at the upper part of the acidification tower; the sodium carbonate solution middle tank is arranged on the ground, the upper feeding pipeline is distributed and connected with the sodium carbonate solution pipelines at the lower parts of the decomposing tower and the acidification tower, and the lower outlet pipeline is connected with the sodium carbonate solution pump inlet pipeline; the sodium carbonate solution pump is arranged on the ground, an inlet pipeline of the sodium carbonate solution pump is connected with an outlet pipeline at the lower part of the sodium carbonate solution middle tank, and the outlet pipeline is connected with a sodium carbonate solution delivery pipeline; the carbon dioxide balance tank is arranged on a high platform, a gas inlet of the carbon dioxide balance tank is connected with a gas converging pipeline of the decomposing tower and the acidification tower top, and a gas outlet of the carbon dioxide balance tank is connected with a gas inlet of the circulating fan; the acidification bubbler is arranged at the bottom of the acidification tower and is connected with a 95% fresh carbon dioxide supply pipeline; the circulating fan is arranged on the ground, the gas inlet is connected with the carbon dioxide balance tank, and the gas outlet is connected with the converging pipeline of the gas inlets at the bottoms of the decomposing tower and the acidifying tower.
The upper part of the carbon dioxide balance tank is provided with a single calling valve and a single suction valve; the diameter and the suction amount of the single suction valve are determined according to the sodium phenolate treatment amount and the concentration of the supplemented fresh carbon dioxide, the designed suction pressure is-500 Pa, and when the system pressure is low, the suction air is used for balancing the system pressure to be not lower than-500 Pa. The diameter and the expiration volume of the single calling valve are also determined according to the treatment capacity of the sodium phenolate and the concentration of the supplemented fresh carbon dioxide, and the single calling valve is designed to have the expiration pressure of +500Pa. The decomposing tower and the acidification tower are one-section towers with two layers of stainless steel pall ring fillers.
In order to balance the pressure of the gas circulation system, a single calling valve and a single suction valve are arranged at the upper part of the carbon dioxide balance tank, and when the system bears positive pressure, the single calling valve opens the exhaled gas to release the positive pressure; when the system is subjected to negative pressure, the single suction valve opens to suck air and release the negative pressure. Thereby ensuring the system pressure within a certain range, ensuring safe operation and reducing the gas emission. The diameter and the air suction amount of the single suction valve are determined according to the sodium phenolate treatment amount and the concentration of the supplemented fresh carbon dioxide, the designed suction pressure is-500 Pa, and when the system pressure is low, the air is sucked to balance the system pressure to be not lower than-500 Pa; the diameter and the expiration amount of the single expiration valve are also determined according to the treatment amount of the sodium phenolate and the concentration of the supplemented fresh carbon dioxide, the expiration pressure of the single expiration valve is designed to be +500Pa, when the system pressure is high, the exhaust gas is burnt in a heating furnace of a tar distillation system (the coking crude phenol production process is to extract phenolic substances from coal tar, and the extraction process needs a tar distillation heating furnace), and the pressure of the system is balanced to be not higher than 500Pa.
The decomposing tower and the acidification tower are one-stage towers with two layers of fillers. The decomposing tower and the acidification tower are made of 304, and the filler is stainless steel (304) pall ring filler. A gas circulation system is established by the decomposing tower, the acidification tower, the carbon dioxide balance tank and the circulating fan, and unreacted gas escaping from the top of the decomposing tower and the acidification tower enters the carbon dioxide balance tank and is conveyed to the bottom of the decomposing tower and the bottom of the acidification tower by the circulating fan for recycling. The acidification bubbler at the outlet of the circulating fan and the bottom of the acidification tower supplements CO with concentration more than 95 percent 2 Gas, maintenance system CO 2 Is a balance of (3).
Using CO at a concentration of greater than 95% 2 Gas as make-up CO 2 Air source and control the recycle gas CO entering the decomposing tower and the acidifying tower 2 The concentration is 15% -20%, and the CO at the bottom of the acidification tower 2 The concentration is 20% -25%. A single suction valve is arranged at the upper part of the carbon dioxide gas balance tank, and when the system pressure is low, air is sucked to balance the system pressure to be not lower than-500 Pa. And a single calling valve is arranged at the upper part of the carbon dioxide gas balance tank, and when the system pressure is high, the discharged gas is burnt in a heating furnace of the tar distillation system so as to balance the system pressure to be not higher than +500Pa.
The invention is suitable for clean production of gas circulation coking crude phenol in the processing and refining process of high-temperature coal tar and medium-low-temperature coal tar, and compared with the prior art, a decomposed gas circulation system is established, and CO with the concentration of more than 95 percent is used 2 Supplementing CO as a gas circulation system 2 Air source, will be manyThe residual small amount of gas is discharged into a heating furnace of a tar distillation system for burning, SO that the equipment corrosion (sulfuric acid decomposition and SO) existing in the existing sodium phenolate decomposition operation is solved 2 Decomposition), short running period (pure CO 2 Decomposition), the tail gas pollutes the environment (flue gas decomposition), and the like, and a small amount of redundant gas is discharged into a heating furnace of a tar distillation system for burning, so that no waste gas is discharged, and long-period operation and clean production are realized. Has the advantages of high automation level, convenient operation, energy conservation, environmental protection, investment conservation, good economic benefit and the like.
Drawings
FIG. 1 is a production flow chart of the present invention;
in the figure: k01 is a decomposition tower, K02 is an acidification tower, P01 is an acidification tower raw material pump, P02 is a sodium carbonate solution pump, B01 is a circulating fan, T01 is a primary crude phenol middle tank, T02 is a sodium carbonate solution middle tank, T03 is a carbon dioxide balance tank, and M01 is an acidification bubbler.
1 is a sodium phenolate inlet, 2 is a fresh carbon dioxide supplementing inlet of an acidification bubbler, 3 is a fresh carbon dioxide supplementing inlet of an outlet of a circulating fan, 4 is a sodium carbonate solution delivery port, and 5 is a product crude phenol outlet.
Detailed description of the preferred embodiments
The method specifically comprises the following steps:
(1) The high-temperature coal tar is distilled to obtain a phenol oil fraction with the phenol content of about 6-8%, the phenol oil fraction is washed by NaOH aqueous solution, and NaOH reacts with phenolic substances to generate a phenol sodium salt solution. Delivering sodium phenolate solution with temperature of 60-80deg.C and concentration of 25% at a flow rate of 1000-1500 kg/hr to the upper part of decomposition tower (K01) with two layers of stainless steel pall ring filler, flowing from top to bottom through the filler layer, and mixing with rising circulating gas (effective component CO 2 ) Reverse contact, CO entering into acidification tower (K02) 2 Controlling the concentration to be about 18%; most of the sodium phenolate is recycled to the CO in the gas 2 To generate crude phenol and sodium carbonate (Na) 2 CO 3 ) Then flows into the bottom of the decomposing tower (K01).
(2) The once decomposed material is prepared under 60-80 ℃ according to the conditions of crude phenol and sodium carbonate (Na 2 CO 3 ) The specific gravity difference is statically separated at the bottom of the decomposing tower (K01) for about 6 hours to finish the crude phenol and Na 2 CO 3 Separation of the solution, separated Na 2 CO 3 The solution flows to a storage tank, and the crude phenol flows to a primary crude phenol middle tank (T01);
(3) The crude phenol obtained by primary decomposition and static separation also contains a part of unreacted phenol sodium salt, and is conveyed to the upper part of an acidification tower (K02) with two layers of stainless steel pall ring fillers by an acidification tower (K02) raw material pump under the pressure of 0.4MPa, flows from top to bottom through a filler layer, and is mixed with circulating gas (active ingredient CO) from the bottom of the tower 2 ) Reverse contact, wherein the sodium phenolate is replaced by CO in the recycle gas 2 After further decomposition, the mixture flows into the bottom of an acidification tower (K02);
(4) In order to make the acidification reaction more thorough, an acidification bubbler (M01) with an injection hole is arranged at the bottom of an acidification tower (K02) and is used for adding CO with concentration of more than 95 percent 2 Bubbling acidification is carried out on the liquid material at the bottom of the acidification tower (K02)
(5) The material after acidification and bubbling is processed at 90-95 ℃ according to crude phenol and sodium carbonate (Na 2 CO 3 ) Standing and separating for about 10 hours to finish the crude phenol and Na 2 CO 3 Separation of the solution, separated Na 2 CO 3 The solution automatically flows to a storage tank, and the crude phenol meets the quality requirement and leaves the factory. The bottoms of the decomposing tower (K01) and the acidifying tower (K02) are provided with indirect heaters, and the temperature of the bottom of the tower is controlled within a required range.
The decomposing tower (K01) and the acidification tower (K02) are both ring-packed towers; the decomposing tower (K01) is arranged on the ground, a top gas pipeline of the decomposing tower is connected with a top gas pipeline of the acidifying tower, a bottom gas pipeline of the decomposing tower is connected with a bottom gas pipeline of the acidifying tower, a bottom primary crude phenol pipeline is connected with a feeding pipeline at the upper part of a primary crude phenol middle tank (T01), and a sodium carbonate solution pipeline at the bottom of the decomposing tower is connected with a feeding pipeline at the upper part of a sodium carbonate solution middle tank (T02); the acidification tower (K02) is arranged on the ground, a crude phenol pipeline at the bottom of the acidification tower is connected with a finished crude phenol pipeline, and a sodium carbonate pipeline at the bottom of the acidification tower is connected with a feeding pipeline at the upper part of a sodium carbonate solution middle tank (T02); the primary crude phenol middle tank (T01) is arranged on the ground, the upper feeding pipeline is connected with the primary crude phenol pipeline at the lower part of the decomposing tower, and the lower outlet pipeline is connected with the raw material pump inlet pipeline of the acidifying tower (K02); the acidification tower (K02) raw material pump is arranged on the ground, an inlet pipeline of the acidification tower is connected with an outlet pipeline at the lower part of the primary crude phenol middle tank (T01), and the outlet pipeline is connected with a feeding pipeline at the upper part of the acidification tower (K02); the sodium carbonate solution middle tank (T02) is arranged on the ground, the upper feeding pipeline of the sodium carbonate solution middle tank is connected with the sodium carbonate solution pipeline at the lower parts of the decomposing tower (K01) and the acidifying tower (K02), and the lower outlet pipeline is connected with the sodium carbonate solution pump (P02) inlet pipeline; the sodium carbonate solution pump (P02) is arranged on the ground, an inlet pipeline of the sodium carbonate solution pump is connected with an outlet pipeline at the lower part of the sodium carbonate solution middle tank (T02), and an outlet pipeline is connected with a sodium carbonate solution delivery pipeline; the carbon dioxide balance tank (T03) is arranged on a high platform, a gas inlet of the carbon dioxide balance tank is connected with a gas converging pipeline at the top of the decomposing tower (K01) and the acidizing tower (K02), and a gas outlet of the carbon dioxide balance tank is connected with a gas inlet of the circulating fan (B01); the acidification bubbler (M01) is arranged at the bottom of the acidification tower (K02) and is connected with a 95% fresh carbon dioxide supply pipeline; the circulating fan (B01) is arranged on the ground, the gas inlet is connected with the carbon dioxide balance tank (T03), and the gas outlet is connected with a converging pipeline at the bottom gas inlets of the decomposing tower (K01) and the acidifying tower (K02).
Unreacted gas escapes from the top of the decomposition tower (K01) and the acidification tower (KO 2) to enter a carbon dioxide balance tank (T03), and is respectively conveyed to the bottom of the decomposition tower (K01) and the bottom of the acidification tower (K02) by a circulating fan (B01) for recycling. The acidification bubbler (M01) at the outlet of the circulating fan (B01) and the bottom of the acidification tower (KO 2) is used for supplementing carbon dioxide (CO) with concentration of more than 95 percent 2 ) Gas, carbon dioxide (CO) of holding system 2 ) Is a balance of (3).
The upper part of the carbon dioxide balance tank (T03) is provided with a single suction valve, and the specification of the single suction valve is as follows: DN80, HXF-DX type, when the system pressure is low, sucking air to balance the system pressure not lower than-500 Pa; the upper part of the carbon dioxide balance tank (T03) is provided with a single calling valve, and the specification of the single sucking valve is as follows: DN80, HXF7 with connection pipe (fire-retardant), when the system pressure is high, the exhaust gas is burned in the heating furnace of the tar distillation system to balance the system pressure not higher than +500Pa; an indirect heater is arranged in the carbon dioxide balance tank (T03), and the temperature of the circulating gas is controlled to be between 60 ℃ and 80 ℃.
Claims (9)
1. A clean production method of gas circulation coking crude phenol is characterized in that:
(1) Distilling high-temperature coal tar or medium-low-temperature coal tar to obtain a phenol oil fraction with the phenol content of 6% -20%, washing the phenol oil fraction in a vertical washing tower with NaOH aqueous solution to remove phenol, and enabling the NaOH aqueous solution and the phenol oil fraction to reversely flow to contact phenol and NaOH to react to generate a phenol sodium salt solution;
(2) Delivering sodium phenolate solution with temperature of 60-80deg.C and concentration of 20-40% to the upper part of decomposition tower with two layers of filler, flowing from top to bottom through the filler layer, and mixing with CO as effective component 2 Is reversely contacted with the recycle gas of CO 2 The concentration is controlled between 15% and 20%, and most of the sodium phenolate is controlled by CO in the circulating gas 2 To generate crude phenol and sodium carbonate (Na) 2 CO 3 ) Then flows into the bottom of the decomposing tower;
(3) According to crude phenol and sodium carbonate (Na 2 CO 3 ) The specific gravity difference of the solution is still separated for 6 to 8 hours to finish the crude phenol and Na 2 CO 3 Separation of the solution, separated Na 2 CO 3 The solution flows to a storage tank automatically, and the crude phenol flows to a primary crude phenol middle tank automatically;
(4) Conveying the primary crude phenol obtained by static separation to the upper part of an acidification tower with two layers of fillers by an acidification tower raw material pump under the pressure of not lower than 0.4MPa, flowing from top to bottom through the filler layers, and mixing with active ingredient CO from the bottom of the tower 2 Wherein the sodium phenolate is reversely contacted by CO in the recycle gas 2 Further decomposing and then flowing into the bottom of the acidification tower;
(5) Unreacted CO 2 The gas escapes from the top of the decomposing tower and the acidification tower, enters a carbon dioxide balance tank, and is respectively conveyed to the bottoms of the decomposing tower and the acidification tower by a circulating fan for recycling, thereby establishing carbon dioxide decompositionIs provided.
2. The method for clean production of gas-circulated coking crude phenol according to claim 1, characterized in that an acidification bubbler with an injection hole is arranged at the bottom of the acidification tower, and CO with concentration higher than 95% is used 2 The gas further bubbling acidizes the liquid material at the bottom of the acidification tower and controls CO in the gas at the bottom of the acidification tower 2 The concentration is 20% -25%; the material after acid bubbling is processed according to crude phenol and sodium carbonate (Na 2 CO 3 ) Standing and separating for 8-10 hr to obtain crude phenol and Na 2 CO 3 Separation of the solution, separated Na 2 CO 3 The solution automatically flows to a storage tank, and the crude phenol meets the quality requirement and leaves the factory.
3. A method for the clean production of gas-cycled coking crude phenol according to claim 1 or 2, characterized in that for maintaining the system CO 2 Is added with CO with concentration more than 95% at the outlet of a circulating fan and an acidification bubbler at the bottom of an acidification tower 2 And (3) gas.
4. The clean production method of gas circulation coking crude phenol according to claim 1 or 2, which is characterized in that for balancing the pressure of a gas circulation system, a single-calling valve and a single-suction valve are arranged at the upper part of a carbon dioxide balance tank body, and when the system bears positive pressure, the single-calling valve opens the exhaled gas to release positive pressure; when the system bears negative pressure, the single suction valve opens the suction air to release the negative pressure; thereby ensuring safe operation of the system pressure within a certain range and reducing the gas discharge.
5. The method for clean production of gas-circulated coking crude phenol according to claim 4, wherein the diameter and the suction amount of the single suction valve are determined according to the sodium phenolate treatment amount and the concentration of the fresh carbon dioxide to be supplemented, the suction pressure is designed to be-500 Pa, and the suction air is designed to balance the system pressure to be not lower than-500 Pa when the system pressure is low.
6. The clean production method of gas circulation coking crude phenol according to claim 4, wherein the diameter and the expiration amount of the single-call valve are determined according to the sodium phenolate treatment amount and the concentration of the supplemented fresh carbon dioxide, the expiration pressure of the single-call valve is designed to be +500Pa, and when the system pressure is high, the gas is discharged to a heating furnace of a tar distillation system for burning, and the system pressure is balanced to be not higher than +500Pa.
7. The gas circulation coking crude phenol clean production device according to claim 1, which is characterized by comprising a decomposition tower, an acidification tower, a primary crude phenol middle tank, an acidification tower raw material pump, a sodium carbonate solution middle tank, a sodium carbonate solution pump, a carbon dioxide balance tank, an acidification bubbler and a circulating fan; the decomposing tower and the acidification tower are all ring packed towers; the decomposing tower is arranged on the ground, a top gas pipeline of the decomposing tower is connected with a top gas pipeline of the acidifying tower, a bottom gas pipeline of the decomposing tower is connected with a bottom gas pipeline of the acidifying tower, a bottom primary crude phenol pipeline is connected with a feeding pipeline at the upper part of a primary crude phenol middle tank, and a bottom sodium carbonate solution pipeline is connected with a feeding pipeline at the upper part of a sodium carbonate solution middle tank; the acidification tower is arranged on the ground, a crude phenol pipeline at the bottom of the acidification tower is connected with a finished crude phenol pipeline, and a sodium carbonate pipeline at the bottom of the acidification tower is connected with a feeding pipeline at the upper part of a sodium carbonate solution middle tank; the primary crude phenol middle tank is arranged on the ground, the upper feeding pipeline is connected with the primary crude phenol pipeline at the lower part of the decomposing tower, and the lower outlet pipeline is connected with the raw material pump inlet pipeline of the acidifying tower; the acidification tower raw material pump is arranged on the ground, an inlet pipeline of the acidification tower raw material pump is connected with an outlet pipeline at the lower part of the primary crude phenol middle tank, and the outlet pipeline is connected with a feeding pipeline at the upper part of the acidification tower; the sodium carbonate solution middle tank is arranged on the ground, the upper feeding pipeline is distributed and connected with the sodium carbonate solution pipelines at the lower parts of the decomposing tower and the acidification tower, and the lower outlet pipeline is connected with the sodium carbonate solution pump inlet pipeline; the sodium carbonate solution pump is arranged on the ground, an inlet pipeline of the sodium carbonate solution pump is connected with an outlet pipeline at the lower part of the sodium carbonate solution middle tank, and the outlet pipeline is connected with a sodium carbonate solution delivery pipeline; the carbon dioxide balance tank is arranged on a high platform, a gas inlet of the carbon dioxide balance tank is connected with a gas converging pipeline of the decomposing tower and the acidification tower top, and a gas outlet of the carbon dioxide balance tank is connected with a gas inlet of the circulating fan; the acidification bubbler is arranged at the bottom of the acidification tower and is connected with a 95% fresh carbon dioxide supply pipeline; the circulating fan is arranged on the ground, the gas inlet is connected with the carbon dioxide balance tank, and the gas outlet is connected with the converging pipeline of the gas inlets at the bottoms of the decomposing tower and the acidifying tower; the decomposing tower and the acidifying tower bottom are provided with indirect heaters to control the tower bottom temperature in the required range.
8. The gas cycle coking crude phenol clean production device according to claim 7, characterized in that the single suction valve specification is of the DN80 and HXF-DX type, and the single suction valve specification is of the DN80 and HXF7 with take-over fire-retardant type.
9. The gas circulation coking crude phenol clean production device according to claim 7, wherein the decomposing tower and the acidifying tower are one-stage tower with two layers of fillers.
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| CN110330408A (en) * | 2019-07-23 | 2019-10-15 | 山西永东化工股份有限公司 | A kind of gas Cycle-decomposition coking crude phenol coproduction light calcium production method |
| CN110590509A (en) * | 2019-09-25 | 2019-12-20 | 山西永东化工股份有限公司 | Production method for carbon dioxide cyclic decomposition coking crude phenol coproduction desulfurizer |
| CN112521253B (en) * | 2020-12-18 | 2023-11-28 | 中冶焦耐(大连)工程技术有限公司 | Carbon dioxide decomposition system and process of sodium phenolate |
| CN112850978A (en) * | 2021-01-19 | 2021-05-28 | 青岛科技大学 | Extraction and electrolysis integration-based treatment method for wastewater in coal tar production |
| CN112939746A (en) * | 2021-02-04 | 2021-06-11 | 中冶焦耐(大连)工程技术有限公司 | Pre-pump mixing tower type continuous washing dephenolizing process |
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| CN102381943A (en) * | 2011-08-30 | 2012-03-21 | 河南宝舜化工科技有限公司 | System and technology for producing coked crude phenol |
| WO2016155101A1 (en) * | 2015-03-31 | 2016-10-06 | 中国科学院过程工程研究所 | System and treatment process for combined removal of phenol oil from phenol-ammonia wastewater |
| CN209508091U (en) * | 2019-01-24 | 2019-10-18 | 山西永东化工股份有限公司 | A kind of gas circulation coking crude phenol cleaning production apparatus |
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| CN102381943A (en) * | 2011-08-30 | 2012-03-21 | 河南宝舜化工科技有限公司 | System and technology for producing coked crude phenol |
| WO2016155101A1 (en) * | 2015-03-31 | 2016-10-06 | 中国科学院过程工程研究所 | System and treatment process for combined removal of phenol oil from phenol-ammonia wastewater |
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