CN1279231A - Process for refining coarse phenol containing sulfur - Google Patents
Process for refining coarse phenol containing sulfur Download PDFInfo
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Abstract
A process for refining sulfur-contained coarse phenol includes two technological routes. One includes such steps as adding oxidant to sulfur-contained coarse phenol, sufficiently oxidizing thiol-type sulfur, vacuum distillation under pressure less than 0.02 MPa and collecting aqueous fraction. Another includes adding alkali solution to sulfur-contained coarse phenol, fully dissolving, adding oxidant, sufficiently oxidizing thiol-type sulfur, separating oil phase from water phase, adding inorganic acid to water phase, separating oil phase from water phase, and distilling oil phase. Its advantages include high desulfurization effect.
Description
The present invention relates to the process for purification of crude phenols, exactly is the process for purification about the coarse phenol containing sulfur that reclaims from the alkaline residue of oil or coal tar.
Contain phenols in the lightweight oil that produces in the petroleum refining process, for example in catalytically cracked gasoline, usually contain 0.01～0.1% phenols, lightweight oil is being carried out alkali cleaning when refining, these phenols major parts enter in the alkaline residue: the phenol content in the coal tar is bigger, often adopts the extractive method of alkali that it is separated, reclaims.The crude phenols that from lightweight oil alkaline residue and coal tar alkaline residue, reclaim (following oil crude phenols and the tar crude phenols of being called for short respectively) mainly consist of water, phenol, adjacent,, p-cresol, dimethylphenol.Reclaim the phenols in lightweight oil alkaline residue and the coal tar alkaline residue, not only help alleviating in the sewage of discharging, can also obtain the very high phenols of industrial application value because of phenol too high levels pollution on the environment.
The phenols that directly reclaims from lightweight oil or coal tar alkaline residue needs further refining, can use after reaching certain specification.The difficult point of process for refining is the sulfocompound (mainly being mercaptan and disulphide) that removes in the crude phenols, because mercaptan itself is extremely smelly, and most disulphide is met heat a little and also can be transformed into and can emit malodorous mercaptan and make it and can't use in the course of processing.The content of sulfocompound alters a great deal with feedstock property and raw material sources in the crude phenols, for example the sulphur content of coal tar crude phenol is lower, usually at 200～2000ppm, the sulphur content of oil crude phenols is higher, generally in 4000～20000ppm (0.4～2.0%), the sulphur content of indivedual oil crude phenols even reach more than the 35000ppm (3.5%).
About making with extra care of phenol, existing at present many methods, but the overwhelming majority is the refining of relevant chemosynthesis phenol, has only minority to relate to the refining of oil crude phenols and tar crude phenols.Desulfurization, the deodorizing technology of oil cresols are disclosed as CN1105657, embodiment is: 2000kg oil crude phenols were obtained 1000kg oil cresols in 10 hours through the normal pressure distillation, after in oil cresols, adding the stirring of 27kg caustic soda earlier, adding the 18kg hydrogen peroxide again stirs, add 27kg sulfuric acid again and stir, made with extra care 8 hours behind the adding emulsion splitter, discharge lower aqueous solution, carry out vacuum distilling 17 hours, and obtained oil cresols product.Facts have proved that the refining cycle of this method is long, deodorising effect is also bad, and caustic soda that is added and hydrogen peroxide do not make mercaptan sulfur remove fully, and the oil crude phenols still have foul smell after this method is handled several times.
JP62-12731 adopts hydrogen peroxide, potassium permanganate, air or ozone that coarse phenol containing sulfur is carried out oxidation, make mercaptan be converted into the less relatively disulphide of stink with foul smell, carry out air distillation then and remove moisture content and heavier impurity, carry out clay-filteredly or rectified purified again, obtain refining phenol.Experiment is found, this method truly has the desulfuration-deodorization effect, but for the higher crude phenols of sulphur content, oil crude phenols particularly, when the mercaptan with foul smell being converted into directly carry out air distillation behind the less relatively disulphide of stink by oxidation, most of disulphide make the desulfuration-deodorization effect be subjected to obvious influence, and follow-up clay-filtered or rectifying all is difficult to remove mercaptan residual in the phenol owing to be subjected to the heat-flash effect in the still-process to be cracked into mercaptan again.Therefore, for sulphur content higher crude phenols raw material, particularly oil crude phenols, this method is difficult to reach the purpose of thorough deodorization.
The objective of the invention is to overcome above-mentioned defective, the process for purification of the coarse phenol containing sulfur that two kinds of effects have improved is provided, realize the desulfuration-deodorization of oil crude phenols and tar crude phenols.
First method provided by the invention is to add oxygenant to make the abundant oxidation of mercaptan sulfur in coarse phenol containing sulfur, carries out underpressure distillation then under ≯ 0.02MPa pressure, and the water after cut of collecting is refining phenol.
Exactly, can implement in the following manner: in coarse phenol containing sulfur, stoichiometric 1～5 times according to mercaptan sulfur content, preferred 1.5～2.5 extraordinarily go into oxygenant, as hydrogen peroxide, and potassium permanganate, ozone or air (O
2) etc., fully behind the mixing, in normal temperature～100 ℃, preferred 30～85 ℃ were reacted 0.5～8 hour down, preferred 1～5 hour, make the abundant oxidation of mercaptan sulfur, then pressure ≯ the 0.02MPa of the hierarchy of control, preferably ≯ 0.01MPa, more preferably ≯ and carry out underpressure distillation under the 0.005MPa, make at the bottom of the still kettle temperature ≯ 200 ℃ preferably to be no more than 180 ℃, collect before the water two groups of fractions behind (moisture) and water, wherein the water after cut is the phenol of having made with extra care.
If hydrogen sulfide content is higher in the crude phenols, the concentration that can add 0.1～0.5 heavy % earlier in crude phenols is 10～30% sodium hydroxide or potassium hydroxide solution, or solid sodium hydroxide or the potassium hydroxide of 0.01～0.03 heavy %, add oxygenant again after waiting to dissolve and carry out oxidizing reaction.
According to the needs of target product, the water after cut can be carried out again one to two time air distillation, cut into fractions such as phenol, cresols, xylenol, in order to follow-up use.Also this step can be moved on to before the oxidation step, promptly directly crude phenols be carried out air distillation and cut boiling range, in each fraction, add oxygenant respectively and carry out oxidizing reaction, underpressure distillation then.
If sulphur content is very high in the crude phenols, can adopt second method provided by the invention, make mercaptan sulfur remove more thoroughly.This method is to add alkali lye in coarse phenol containing sulfur, make crude phenols be dissolved in the alkali lye fully, add oxygenant and make the abundant oxidation of mercaptan sulfur, separate oil phase and water then, adding mineral acid at aqueous phase makes phenates be reduced to phenol, separate oil phase and water again, oil phase is distilled, can obtain refining phenol.
Exactly, can implement in the following manner: (1) is in coarse phenol containing sulfur, according to 1～2.5 times of the stoichiometry of phenol, preferred 1～1.5 extraordinarily goes into alkali, as concentration is 5～30%, and preferred 10～20% NaOH or KOH solution make crude phenols be converted into phenates fully and is dissolved in the alkali lye; (2) then stoichiometric 1～5 times according to mercaptan sulfur content, preferred 1.5～2.5 extraordinarily go into oxygenant, as hydrogen peroxide, potassium permanganate, ozone or air etc., fully behind the mixing, in normal temperature～100 ℃, preferred 30～85 ℃ were reacted 0.5～8 hour down, preferred 1～5 hour, make mercaptan sulfur fully be oxidized to the disulphide that is insoluble to alkali lye; (3) separate oil phase and water then, can be natural subsidence 4～72 hours, or with whizzer centrifugal settling, or carry out extracting with solvent oil such as sherwood oil, or aforesaid method is united use so that separate more thoroughly, carry out acidifying at the aqueous phase adding mineral acid such as sulfuric acid, hydrochloric acid or other mineral acid that obtain, make phenates be reduced to oil-soluble phenol, again water and the oil phase that produces after natural subsidence or the centrifugation acidifying; (4) oil phase is carried out air distillation, or rationally cut boiling range as required, can obtain all kinds of phenolic products that sulphur content is extremely low, smell is normal, up-to-standard.
Also can reverse step (1) and (2), promptly in crude phenols, add oxygenant earlier and carry out oxidizing reaction, make the abundant oxidation of mercaptan sulfur, add alkali lye again, crude phenols are dissolved in the alkali lye fully.
In step (1) before, also can directly carry out one to the several air distillation to crude phenols, and rationally cut boiling range according to the needs of target product, obtain fractions such as phenol, cresols, xylenol, add oxygenant, alkali lye and mineral acid respectively according to step (1), (2) and (3) in each fraction then, obtaining after the separation with water is all kinds of phenol of major impurity.Respectively these phenol are distilled, preferably carry out underpressure distillation,, can obtain the various qualified phenolic product of almost completely desulfurization to remove moisture content and a small amount of high-boiling-point impurity.
The process for purification of two kinds of coarse phenol containing sulfurs provided by the invention be to the various ingredients in the crude phenols particularly impurity carried out drawing on the basis of abundant research.Wherein the characteristics of first method are that the oxygenant that adds q.s earlier makes mercaptan sulfur fully be oxidized to the higher disulphide of boiling point, and the lower system pressure of control makes it not decompose in still-process and stays at the bottom of the still again, thereby reach the purpose of desulfuration-deodorization.The characteristics of second method are that the alkali lye that adds q.s makes phenol be converted into phenates fully and is dissolved in the alkali lye, the adding oxygenant makes the mercaptan that is dissolved in alkali lye be converted into insoluble disulphide and removes, again the phenates acidifying is reduced to phenol, also reaches the purified purpose.
The process for purification desulfuration-deodorization of two kinds of coarse phenol containing sulfurs provided by the invention is effective, can obtain low, the no stink of sulphur content, up-to-standard all kinds of phenolic products.
The invention will be further described below by example.
In the following example, mercaptan sulfur content is pressed the test of GB/T1792 method, and the stoichiometry of phenol is calculated (because cresols is the main body in the crude phenols) with crude phenols weight divided by the cresols molecular weight.Example 1
A kind of oil crude phenols are packed in the still kettle, directly carry out an air distillation, remove＜180 ℃ fraction, collect 180～190 ℃ (major ingredient is a phenol), the fraction of 190～208 ℃ (main component is a cresols) and 208-225 ℃ (major ingredient is an xylenol), measure mercaptan sulfur content and be respectively 5000pp, 2200ppm and 3400ppm, in each fraction, add concentration and be about 30% hydrogen peroxide for stoichiometric 1.5 times by each fraction mercaptan sulfur content, be warming up to 75 ℃, reacted 4 hours, and made the abundant oxidation of mercaptan sulfur of each fraction.Each raw material of then hydrogen peroxide being handled is respectively charged in the underpressure distillation still, the pressure of elder generation's hierarchy of control is at 0.02MPa, distillation removes＜reduce pressure to 0.005 MPa of system behind 100 ℃ the fraction again, for temperature ≯ 160 at the bottom of the phenol control still ℃, for temperature ≯ 170 at the bottom of the cresols control still ℃, for temperature ≯ 190 at the bottom of the xylenol control still ℃, carry out underpressure distillation, obtain lower, the no stink of sulphur content, up-to-standard all kinds of phenolic products.The character of raw materials used and refining back phenol products sees Table 1.
Table 1
| Test event | Outward appearance | Smell | Moisture, % | Boiling range | Sulphur content, ppm | Nitrogen content, ppm | Neutral oil, % | ||
| Crude phenols | Black | Extremely smelly | 10 | ?／ | ??4000 | ??46 | ?／ | ||
| Refining phenol | Phenol | Colourless | The phenol flavor | 0．7 | ??／ | ??30 | ??0 | ??1．1 | |
| Cresols | Pale yellow | The phenol flavor | 0．6 | Qualified | ??75 | ??6 | ??0．6 | ||
| Xylenol | Brown | The phenol flavor | 0．2 | Qualified | ??15 | ??0．7 | |||
| Testing method | YB2301 —78 | ?／ | ?GB2288 —80 | ?GB2282 —80 | The microcoulomb method | The microcoulomb method | GB2603— ????81 | ||
Example 2
The character of used oil crude phenols is as shown in table 2.In this oil crude phenols of portion, add the concentration that accounts for crude phenols gross weight 0.5% and be about 30% sodium hydroxide liquid caustic soda, add the concentration that accounts for crude phenols gross weight 1.0% again and be about 30% hydrogen peroxide, fully behind the mixing, reacted 4 hours down, make the abundant oxidation of mercaptan sulfur of reaction product in 70 ℃.Raw material after will handling is then packed in the still kettle, the pressure of elder generation's hierarchy of control is at 0.02 MPa, carry out underpressure distillation, remove＜100 ℃ fraction (based on moisture), reduce pressure to 0.01 MPa of system then, proceed underpressure distillation, the pressure that progressively reduces system is to≤0.005MPa, and temperature is all the time ≯ 190 ℃ at the bottom of the control still, merge all fractions except that moisture, it is carried out air distillation, collect 180～225 ℃ fraction, then this section fraction is further carried out air distillation, collect 180～190 ℃, 190～206 ℃, 206～225 ℃ fraction, measure mercaptan sulfur content and be respectively 60000pp, 18000ppm and 21000ppm, in each fraction, add concentration and be about 30% hydrogen peroxide for stoichiometric 2 times by each fraction mercaptan sulfur content, be warming up to 80 ℃ gradually, reacted 8 hours, make the abundant oxidation of mercaptan sulfur, again respectively after dehydration under the vacuum condition of 0.02 MPa, further reduce system pressure to≤0.005MPa, be no more than 170 ℃ for temperature at the bottom of the phenol control still, be no more than 180 ℃ for temperature at the bottom of the cresols control still, be no more than 200 ℃ for temperature at the bottom of the xylenol control still, carry out underpressure distillation, obtain low-sulfur, no stink, up-to-standard all kinds of phenolic products.The character of oil crude phenols raw material and refining back product is as shown in table 2.
Table 2
| Test event | Outward appearance | Smell | Moisture | Boiling range | Sulphur content, ppm | Nitrogen contains puts ppm | Neutral oil, % | |
| Crude phenols | Black | Extremely smelly | 13 | ／ | 35000 | 76 | ／ | |
| Refining phenol | Phenol | Colourless | The phenol flavor | 0．8 | ／ | 42 | 2 | 1．0 |
| Cresols | Pale yellow | The phenol flavor | 0．6 | Qualified | 138 | 16 | 0．5 | |
| Xylenol | Yellow | The phenol flavor | 0．3 | Qualified | 256 | 25 | 0．8 | |
| Testing method | YB2301 —78 | ／ | ?GB2288 —80 | ?GB2282 —80 | The microcoulomb method | The microcoulomb method | GB2603—81 | |
Example 3
A kind of tar crude phenols are packed in the still kettle, directly carry out an air distillation, remove＜180 ℃ fraction, collect 180～190 ℃ (main component is a phenol), the fraction of 190～208 ℃ (major ingredient is a cresols) and 208～225 ℃ (main component is an xylenol), measure mercaptan sulfur content and be respectively 2400ppm, 1600ppm and 2100ppm, in each fraction, add concentration and be about 30% hydrogen peroxide for stoichiometric 2 times by each fraction mercaptan sulfur content, be warming up to 80 ℃, reacted 2 hours, and made the abundant oxidation of mercaptan sulfur of each fraction.Each raw material of then hydrogen peroxide being handled is respectively charged in the underpressure distillation still, the pressure of elder generation's hierarchy of control is at 0.02 MPa, distillation removes＜100 ℃ fraction after, the pressure that reduces system again is to≤0.005MPa, for temperature ≯ 160 at the bottom of the phenol control still ℃, for temperature ≯ 180 at the bottom of the cresols control still ℃, for temperature ≯ 200 at the bottom of the xylenol control still ℃, carry out underpressure distillation, obtain very low, the no stink of sulphur content, up-to-standard phenol.The character of the different phenol of used tar crude phenols raw material and refining back is referring to table 3.
Table 3
| Test event | Outward appearance | Smell | Moisture content | Boiling range | Sulphur content, ppm | Nitrogen content, ppm | Neutral oil, % | |
| Crude phenols | Black | Extremely smelly | 11％ | ／ | 2000 | 48 | ／ | |
| Refining phenol | Phenol | Colourless | The phenol flavor | 0．8％ | ／ | 5 | 0 | 0．5 |
| Cresols | Yellow | The phenol flavor | 0．5％ | Qualified | 16 | 3 | 0．7 | |
| Xylenol | Brown | The phenol flavor | 0．2％ | Qualified | 30 | 14 | 0．9 | |
| Testing method | YB2301 —78 | ／ | GB2288 —80 | ?GB2282 —80 | The microcoulomb method | The microcoulomb method | GB2603—81 | |
Example 4
Get the oil crude phenols raw material (mercaptan sulfur content is 3000ppm) of 1 part of (weight) sulphur content 2%, the NaOH solution that adds 4 parts of (weight) 12%, after treating that crude phenols are dissolved in alkali lye fully, in system, add the stoichiometric 1.5 times hydrogen peroxide of mercaptan sulfur content again, be warming up to 65 ℃, reacted 5 hours.30～60 sherwood oils with 0.2 part (weight) carry out 3 extractings then, and extracting solution is after sherwood oil is reclaimed in simple distillation, and remaining extract is the sulfide enriched material, and its character sees Table 4; Raffinate with the direct acidifying of industrial sulphuric acid after, phenol sodium is converted into the phenol that is insoluble in water again, enters oil phase from water, sedimentation 4 hours separates upper oil phase (phenol).Oil phase is adopted air distillation, collect 180～190 ℃, 190～206 ℃, 206～225 ℃ fraction, these three sections fractions are carried out underpressure distillation respectively by the condition of example 1 or 2, obtain all kinds of phenolic products that sulphur content is extremely low, smell is normal, up-to-standard, as shown in table 4.
Table 4
| Test event | Outward appearance | Smell | Moisture | Boiling range | Sulphur content, ppm | Nitrogen content, ppm | Neutral oil, % | |
| Crude phenols | Black | Extremely smelly | 11 | ／ | 20000 | 60 | ／ | |
| Refining phenol | Phenol | Colourless | The phenol flavor | 0．8 | ／ | 5 | 1 | 0．1 |
| Cresols | Yellowish | The phenol flavor | 0．5 | Qualified | 21 | 7 | 0．1 | |
| Xylenol | Pale yellow | The phenol flavor | 0．2 | Qualified | 53 | 34 | 0．2 | |
| Extract | Dark-brown | Smelly | ／ | ／ | ?230，000 | ／ | ／ | |
| Testing method | YB2301 —78 | ?／ | ?GB2288 —80 | ?GB2282 —80 | The microcoulomb method | The microcoulomb method | GB2603—81 | |
Claims (10)
1. the process for purification of coarse phenol containing sulfur is characterized in that, adds oxygenant and make the abundant oxidation of mercaptan sulfur in coarse phenol containing sulfur, carries out underpressure distillation under ≯ 0.02MPa pressure, and the water after cut of collecting is refining phenol.
2. according to the described process for purification of claim 1, it is characterized in that oxygenant is selected from hydrogen peroxide, potassium permanganate, ozone or air, the add-on of oxygenant is stoichiometric 1～5 times of a mercaptan sulfur content in the crude phenols.
3. according to the described process for purification of claim 1, it is characterized in that oxidizing condition is normal temperature～100 ℃ following reaction 0.5～8 hour.
4. according to the described process for purification of claim 1, it is characterized in that the pressure of system is ≯ 0.01MPa during underpressure distillation.
5. the process for purification of coarse phenol containing sulfur, it is characterized in that, in coarse phenol containing sulfur, add alkali lye, crude phenols are dissolved in the alkali lye fully, add oxygenant again and make the abundant oxidation of mercaptan, separate oil phase and water, adding mineral acid at aqueous phase makes phenates be reduced to phenol, separate oil phase and water again, oil phase is distilled, can obtain refining phenol.
6. according to the described process for purification of claim 5, it is characterized in that, in coarse phenol containing sulfur, extraordinarily go into alkali lye according to the stoichiometry 1～2.5 of phenol.
7. according to the described process for purification of claim 5, it is characterized in that alkali lye is the NaOH or the KOH solution of concentration 5～30%.
8. according to the described process for purification of claim 5, it is characterized in that oxygenant is selected from hydrogen peroxide, potassium permanganate, ozone or air, the add-on of oxygenant is stoichiometric 1～5 times of a mercaptan sulfur content in the crude phenols.
9. according to the described process for purification of claim 5, it is characterized in that oxidizing condition is normal temperature～100 ℃ following reaction 0.5～8 hour.
10. according to the described process for purification of claim 5, it is characterized in that the separation method of oil phase and water is natural subsidence, centrifugal settling or solvent extraction.
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| CN101704726A (en) * | 2009-11-06 | 2010-05-12 | 天津美科泰化工科技有限公司 | Continuous refinement separation device and method of coked crude phenol |
| CN102153449A (en) * | 2011-03-15 | 2011-08-17 | 天津美科泰化工科技有限公司 | Continuous refining separation device and method for coal gasification crude phenol |
| CN102381932A (en) * | 2010-08-31 | 2012-03-21 | 中国石油化工股份有限公司 | Phenol oxidation method |
| CN105294940A (en) * | 2014-06-23 | 2016-02-03 | 上海宝钢化工有限公司 | Method for removing mercaptan from coumarone resin |
| CN105949096A (en) * | 2016-05-19 | 2016-09-21 | 湖北鼎龙化学股份有限公司 | Optical spectacle lens material, refined polythiol and post-treatment method of crude polythiol |
| CN106008171A (en) * | 2011-10-27 | 2016-10-12 | 沙特基础全球技术有限公司 | Process for producing bisphenol A with reduced sulfur content |
| US9771452B2 (en) | 2012-02-29 | 2017-09-26 | Sabic Global Technologies B.V. | Plastic composition comprising a polycarbonate made from low sulfur bisphenol A, and articles made therefrom |
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| CN114522434A (en) * | 2022-03-15 | 2022-05-24 | 安徽海华科技集团有限公司 | System and process for deep desulfurization of m-cresol |
| CN114874077A (en) * | 2022-05-24 | 2022-08-09 | 安徽海华科技集团有限公司 | Method for deodorizing coking phenol |
| CN115260003A (en) * | 2022-07-22 | 2022-11-01 | 煤炭科学技术研究院有限公司 | Coal pyrolysis/gasification crude phenol impurity removal method and impurity removal system |
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| JPS6041630A (en) * | 1983-08-15 | 1985-03-05 | Kawasaki Steel Corp | Purification of tar acid |
| JPS6216443A (en) * | 1985-07-12 | 1987-01-24 | Nippon Steel Chem Co Ltd | Method of purifying phenol |
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| CN101704726B (en) * | 2009-11-06 | 2013-01-23 | 天津美科泰化工科技有限公司 | Continuous refinement separation device and method of coked crude phenol |
| CN102381932A (en) * | 2010-08-31 | 2012-03-21 | 中国石油化工股份有限公司 | Phenol oxidation method |
| CN102381932B (en) * | 2010-08-31 | 2013-12-25 | 中国石油化工股份有限公司 | Phenol oxidation method |
| CN102153449A (en) * | 2011-03-15 | 2011-08-17 | 天津美科泰化工科技有限公司 | Continuous refining separation device and method for coal gasification crude phenol |
| CN102153449B (en) * | 2011-03-15 | 2013-11-27 | 天津美科泰化工科技有限公司 | Continuous refining separation device and method for coal gasification crude phenol |
| US9957351B2 (en) | 2011-08-05 | 2018-05-01 | Sabic Global Technologies B.V. | Polycarbonate compositions having enhanced optical properties, methods of making and articles comprising the polycarbonate compositions |
| CN106008171A (en) * | 2011-10-27 | 2016-10-12 | 沙特基础全球技术有限公司 | Process for producing bisphenol A with reduced sulfur content |
| US9771452B2 (en) | 2012-02-29 | 2017-09-26 | Sabic Global Technologies B.V. | Plastic composition comprising a polycarbonate made from low sulfur bisphenol A, and articles made therefrom |
| CN105294940A (en) * | 2014-06-23 | 2016-02-03 | 上海宝钢化工有限公司 | Method for removing mercaptan from coumarone resin |
| CN105294940B (en) * | 2014-06-23 | 2018-06-08 | 上海宝钢化工有限公司 | Method for removing mercaptan from coumarone resin |
| CN105949096A (en) * | 2016-05-19 | 2016-09-21 | 湖北鼎龙化学股份有限公司 | Optical spectacle lens material, refined polythiol and post-treatment method of crude polythiol |
| CN114522434A (en) * | 2022-03-15 | 2022-05-24 | 安徽海华科技集团有限公司 | System and process for deep desulfurization of m-cresol |
| CN114522434B (en) * | 2022-03-15 | 2024-06-28 | 安徽海华科技集团有限公司 | Meta-cresol deep desulfurization system and process |
| CN114874077A (en) * | 2022-05-24 | 2022-08-09 | 安徽海华科技集团有限公司 | Method for deodorizing coking phenol |
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