CN113443977B - Sulfur and chlorine removal process in 2-ethyl anthraquinone production - Google Patents
Sulfur and chlorine removal process in 2-ethyl anthraquinone production Download PDFInfo
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- CN113443977B CN113443977B CN202110719187.0A CN202110719187A CN113443977B CN 113443977 B CN113443977 B CN 113443977B CN 202110719187 A CN202110719187 A CN 202110719187A CN 113443977 B CN113443977 B CN 113443977B
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Abstract
The invention discloses a process for removing sulfur and chlorine in 2-ethyl anthraquinone production, and belongs to the technical field of extract liquor treatment in 2-ethyl anthraquinone production. The invention comprises the following steps: (1) mixed alkali washing; (2) preheating alkali washing; (3) heating and alkali washing; (4) oil-water layering; (5) washing an oil layer with water; (6) filtering the oil layer; (7) washing and layering; (8) distilling the solvent; and (9) refining the product. The process can obviously improve the effects of sulfur removal and chlorine removal in the production process of 2-ethylanthraquinone.
Description
Technical Field
The invention relates to the technical field of extract liquor treatment in 2-ethyl anthraquinone production, in particular to a process for removing sulfur and chlorine in 2-ethyl anthraquinone production.
Background
2-ethyl anthraquinone is an important working carrier in hydrogen peroxide production, and the most mature synthesis process route at home and abroad at present is as follows: phthalic anhydride and ethylbenzene are prepared by performing F-C reaction by using chlorobenzene as a solvent and anhydrous aluminum trichloride as a catalyst, and then cyclizing and purifying by fuming sulfuric acid. Because the synthesis process route is long, the side reaction is difficult to control, and the finished product inevitably contains organic impurities of sulfur and chlorine, and although the content of the organic impurities of sulfur and chlorine is low, the palladium catalyst used in the hydrogen peroxide production is poisoned. Therefore, the research on how to reduce the organic impurities of sulfur and chlorine in the 2-ethylanthraquinone to make the organic impurities meet the production requirement of hydrogen peroxide is very significant.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a process for removing sulfur and chlorine in the production of 2-ethylanthraquinone, and the process can obviously improve the effects of sulfur and chlorine removal in the production process of 2-ethylanthraquinone.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a process for removing sulfur and chlorine in the production of 2-ethyl anthraquinone comprises the following steps:
(1) Mixed alkali washing: 1 to 5 mass percent of1m of liquid alkali 3 H is mixed with the extract liquor of the sulfur and chlorine to be removed by 1.5m 3 Carrying out mixed alkaline washing for 1-1.5 h;
(2) Preheating and alkali washing: carrying out preheating alkali washing on the material subjected to mixed alkali washing, and stirring to remove impurities, wherein the preheating alkali washing temperature is 70-80 ℃, and the preheating alkali washing time is 0.5-1 h;
(3) Heating and alkali washing: heating and alkali washing the material subjected to the preheating and alkali washing, wherein the heating and alkali washing temperature is 100-110 ℃, and the heating and alkali washing time is 0.5-1 h;
(4) Oil-water separation: performing oil-water separation on the material subjected to temperature-rising alkali washing, and removing a water layer and an oil layer;
(5) Washing an oil layer with water: stirring and washing the oil layer obtained in the step (4), standing for layering, removing a water layer, and taking the oil layer;
(6) Filtering an oil layer: filtering the oil layer obtained in the step (5) to remove impurities;
(7) Washing and layering: the oil layer obtained by the treatment in the step (6) enters the middle lower part of a washing tower, hot water is added from the middle upper part of the washing tower, the two phases are in countercurrent contact, the materials are automatically discharged in a layered mode by means of different density differences of the materials and design of a U-shaped pipe, the oil layer is formed in the upper part of the tower, and waste water is discharged from the lower part of the tower;
(8) Solvent distillation: heating the oil layer obtained by the treatment in the step (7) under normal pressure to distill most of the extracting agent toluene, heating under reduced pressure to distill the residual extracting agent toluene to obtain a crude product of 2-ethylanthraquinone;
(9) And (3) refining a product: transferring the 2-ethyl anthraquinone crude product into a refining distillation kettle, grinding caustic soda flakes into powder, adding the caustic soda powder into the refining distillation kettle for three times during feeding the 2-ethyl anthraquinone crude product, uniformly stirring, and carrying out high-temperature reduced pressure distillation for 12-13h to complete the processes of sulfur removal and chlorine removal in the production of 2-ethyl anthraquinone.
Further, in the step (2) and the step (3), the heating process of the preheating alkali washing and the heating alkali washing is heating by using waste heat steam, wherein the waste heat steam refers to hot steam recovered from a chlorobenzene distillation system and a toluene distillation system.
Further, in the step (8), the heating atmospheric distillation is carried out at 111-115 ℃ under atmospheric pressure; the heating reduced pressure distillation is carried out under the conditions of 100-130 ℃ and-85 KPa.
Further, in the step (9), the high-temperature reduced-pressure distillation is carried out under the conditions of 200-230 ℃ and less than 100Pa, and the high-temperature reduced-pressure distillation time is 12-13h.
Further, in the step (9), the addition amount of the powdered alkali is 1.0-1.5Kg of powdered alkali per ton of crude 2-ethyl anthraquinone product.
Further, in the step (9), the caustic soda powder is added into the refining distillation kettle in three times, the addition amount is the same every time, the addition is performed once when the refining distillation kettle feeds to 1/3 of the liquid level, the addition is performed once when the refining distillation kettle feeds to 1/2 of the liquid level, and the addition is performed once when the refining distillation kettle finishes feeding. The specific alkali adding amount is determined according to the sulfur and chlorine content of the product.
Further, the sulfur and chlorine removal process is carried out in a sulfur and chlorine removal system in the production of 2-ethylanthraquinone, and the sulfur and chlorine removal system in the production of 2-ethylanthraquinone comprises an alkali washing part, a water washing part, a distillation part and a crude product treatment part:
the alkaline washing part comprises an alkaline washing mixing kettle, an alkaline washing preheating kettle, an alkaline washing warming kettle and an alkaline washing separation tower, wherein a discharge port of the alkaline washing mixing kettle is connected with a feed port of the alkaline washing preheating kettle, a discharge port of the alkaline washing preheating kettle is connected with a feed port of the alkaline washing warming kettle, and a discharge port of the alkaline washing warming kettle is connected with a feed port of the alkaline washing separation tower;
the washing part comprises a washing kettle, a washing filter, a washing tower and a washing oil layer storage tank, wherein a feeding port of the washing kettle is connected with a discharging port of the alkaline washing separation tower, a discharging port of the washing kettle is connected with a feeding port of the washing filter, a discharging port of the washing filter is connected with a feeding port of the washing tower, and a discharging port of the washing tower is connected with a feeding port of the washing oil layer storage tank;
the distillation part comprises a climbing-film evaporator, a climbing-film separation tank and a thin-film evaporator, a feed port of the climbing-film evaporator is connected with a discharge port of the water-washed oil layer storage tank, a discharge port of the climbing-film evaporator is connected with a feed port of the climbing-film separation tank, and a discharge port of the climbing-film separation tank is connected with a feed port of the thin-film evaporator;
the crude product treatment part comprises a refined distillation still and a refined finished product kettle, a feed inlet of the refined distillation still is connected with a discharge outlet of the thin film evaporator, and a discharge outlet of the refined distillation still is connected with a feed inlet of the refined finished product kettle;
the process steps for removing sulfur and chlorine by adopting the sulfur and chlorine removal system in the production of 2-ethyl anthraquinone are as follows: transferring the extract liquor and the caustic soda liquid to be subjected to sulfur and chlorine removal into a caustic washing mixing kettle for mixed caustic washing; after being treated by an alkali washing mixing kettle, the materials are transferred to an alkali washing preheating kettle for preheating and alkali washing; transferring the material treated by the alkali washing preheating kettle to an alkali washing temperature rising kettle for heating and alkali washing, transferring the material treated by the alkali washing temperature rising kettle to an alkali washing separation tower for oil-water separation, transferring an oil layer obtained after the treatment of the alkali washing separation tower into a water washing kettle for water washing, transferring the oil layer obtained after the water washing to a water washing filter for filtration, transferring the oil layer obtained after the filtration into the water washing tower for water washing, transferring the obtained oil layer to a water washing oil layer storage tank, transferring the oil layer to a climbing film evaporator for heating and atmospheric distillation treatment, transferring the treated material to a climbing film separation tank for treatment, and transferring the treated material to a film evaporator for heating and reduced pressure distillation to obtain a 2-ethyl anthraquinone crude product; and transferring the 2-ethyl anthraquinone crude product into a refined distillation kettle for refining, and transferring into a refined product kettle for storage to finish the processes of removing sulfur and chlorine.
Further, the alkali washing part also comprises an alkali washing mixing kettle circulating pump; the circulating pump of the alkaline washing mixing kettle is connected with the bottom of the alkaline washing mixing kettle, the top of the alkaline washing mixing kettle is provided with a mixer connected with the alkaline washing mixing kettle, the circulating pump of the alkaline washing mixing kettle is respectively connected with the liquid alkali supply device and the mixer, and the circulating pump of the alkaline washing mixing kettle is positioned between the liquid alkali supply device and the mixer; the mixer is connected with an extraction liquid supply device to obtain extraction liquid to be subjected to sulfur and chlorine removal, and the extraction liquid subjected to sulfur and chlorine removal and liquid caustic soda are mixed in the mixer and then transferred into a caustic washing mixing kettle.
Further, the alkaline washing part also comprises a toluene tail gas condenser; and the toluene tail gas condenser is connected with a gas outlet of the alkali washing warming kettle.
The reaction principle of the invention is as follows:
1. alkali washing is an extremely important measure for improving the purity of 2-ethylanthraquinone, and can remove the non-ring-closed BE acid and part of the by-products by forming soluble sodium salts. The main factors influencing the alkaline cleaning effect are the alkali concentration, the alkaline cleaning temperature and the alkaline cleaning time. Organic sulfur, organic chlorine and other impurities are dissolved in alkali liquor and separated and removed from anthraquinone, and the reaction formula is as the following formula (1) and formula (2):
2. experimental results show that when the alkaline washing temperature is too low (less than 50 ℃), the viscosity of the material is high, the sulfur and chlorine removal effect is poor, the temperature is gradually increased, the sulfur and chlorine removal effect is more obvious, but when the temperature is too high, toluene in the system is vaporized, the operation risk is increased, and therefore the optimal alkaline washing temperature is 100-110 ℃.
The invention has the beneficial effects that:
the extraction liquid is firstly subjected to alkaline washing, the three steps of mixed alkaline washing, preheating alkaline washing and heating alkaline washing are carried out in the alkaline washing process, and meanwhile, the proper alkaline washing temperature and time are set in each alkaline washing stage, so that the sulfur and chlorine removal effects are obviously improved; the materials after the alkali washing are washed and filtered, and the washing and filtering stage is used for further removing impurities and ensuring that the materials are washed to be neutral, so that the effect is obvious; and (3) sequentially distilling the washed materials by a climbing-film evaporator and a thin-film evaporator in a distillation part, and treating the materials by a refined distillation kettle and the like in a crude product treatment part to obtain the finished product with extremely low sulfur content and chlorine content. After the sulfur and chlorine removal by the process, the sulfur content in the 2-ethyl anthraquinone product is reduced by 60-80% compared with the national standard, and the chlorine content is reduced by 50-70% compared with the national standard; the floccules in the 2-ethyl anthraquinone product are reduced by 50 to 60 percent.
In the mixed alkaline washing stage, the mixer is used for replacing a motor for stirring, so that energy is saved and consumption is reduced; in the preheating alkali washing stage and the heating alkali washing stage, waste heat steam is used for heating, waste heat is recovered, the purposes of energy saving and consumption reduction are achieved, and the steam unit consumption is reduced by 10-15%.
The process can prolong the service life of equipment and the cleaning period, prevent the material from corroding the equipment by acid, and adjust the cleaning period of the equipment from once every quarter to once every half year.
Drawings
FIG. 1 is a schematic diagram of a sulfur and chlorine removal system in the production of 2-ethylanthraquinone in the present invention.
Detailed Description
The invention is further described with reference to the following figures and specific examples.
Example 1
The process comprises the following steps of (1) carrying out a sulfur removal and chlorine removal process in the production of 2-ethylanthraquinone in a sulfur removal and chlorine removal system in the production of 2-ethylanthraquinone, wherein the sulfur removal and chlorine removal system in the production of 2-ethylanthraquinone comprises an alkali washing part, a water washing part, a distillation part and a crude product treatment part, and as shown in figure 1, the process specifically comprises the following steps:
the alkaline washing part comprises an alkaline washing mixing kettle 1, an alkaline washing preheating kettle 3, an alkaline washing heating kettle and an alkaline washing separation tower 10; the upper end of the alkaline washing mixing kettle 1 is provided with a discharge hole and an air outlet, the upper ends of the alkaline washing preheating kettle 3 and the alkaline washing heating kettle are respectively provided with a feed hole, the lower ends of the alkaline washing preheating kettle 3 and the alkaline washing heating kettle are respectively provided with a discharge hole, the lower end of the alkaline washing separation tower 10 is provided with a feed hole, and the upper end of the alkaline washing separation tower 10 is provided with a discharge hole and an air outlet; the discharge port of the alkaline washing mixing kettle 1 is connected with the feed port of the alkaline washing preheating kettle 3, the gas outlets of the alkaline washing mixing kettle 1 and the alkaline washing separation tower 10 are connected with a toluene tail gas condensation recovery device, the toluene tail gas condensation recovery device is a toluene condenser, the discharge port of the alkaline washing preheating kettle 3 is connected with the feed port of the alkaline washing warming kettle, and the discharge port of the alkaline washing warming kettle is connected with the feed port of the alkaline washing separation tower 10.
The alkali washing part also comprises an alkali washing mixing kettle circulating pump 2; the circulating pump 2 of the alkaline washing mixing kettle is connected with the bottom of the alkaline washing mixing kettle 1, the top of the alkaline washing mixing kettle 1 is provided with a mixer connected with the alkaline washing mixing kettle 1, the circulating pump 2 of the alkaline washing mixing kettle is respectively connected with an alkaline solution supply device and the mixer, and the circulating pump 2 of the alkaline washing mixing kettle is positioned between the alkaline solution supply device and the mixer; the mixer is connected with an extraction liquid supply device to obtain extraction liquid. The extraction liquid is the solution of crude anthraquinone toluene, which is the raw material to be treated, and is directly transferred to the mixer by the extraction liquid supply equipment, the liquid caustic soda is pumped to the mixer by the circulation pump 2 of the alkaline washing mixing kettle, and the liquid caustic soda and the extraction liquid are transferred to the alkaline washing mixing kettle 1 after being mixed in the mixer. The alkali washing mixing kettle circulating pump 2 is also used as an external circulating pump of the alkali washing mixing kettle 1, materials in the alkali washing mixing kettle 1 are pumped out from the bottom and sent back to the mixer, and then enter the alkali washing mixing kettle 1, so that the extraction liquid and the liquid alkali are mixed more fully, and the treatment effect is better.
The alkali washing part further comprises an alkali washing warming kettle circulating pump, the alkali washing warming kettle circulating pump comprises a first alkali washing warming kettle circulating pump 6 and a second alkali washing warming kettle circulating pump 7, and the alkali washing warming kettle comprises a first alkali washing warming kettle 4 and a second alkali washing warming kettle 5 which are connected in parallel; the first alkali washing warming kettle circulating pump 6 is connected with a discharge hole of the first alkali washing warming kettle 4, the second alkali washing warming kettle circulating pump 7 is connected with a discharge hole of the second alkali washing warming kettle 5, and the first alkali washing warming kettle circulating pump 6 and the second alkali washing warming kettle circulating pump 7 are both connected with a feed inlet of the alkali washing separating tower 10. And the alkali washing heating kettle circulating pump are correspondingly arranged in two so as to be switched to use at any time.
The alkaline washing part also comprises a first toluene tail gas condenser 8 and a second xylene tail gas condenser 9; the first toluene tail gas condenser 8 is connected with a gas outlet of the first alkali washing warming kettle 4, and the second xylene tail gas condenser 9 is connected with a gas outlet of the second alkali washing warming kettle 5; the gas outlet of the first toluene tail gas condenser 8 and the gas outlet of the second xylene tail gas condenser 9 are both connected with a toluene tail gas condensation and recovery device, the toluene tail gas condenser is used for collecting toluene tail gas generated by the alkali washing warming kettle, and the toluene tail gas condenser is correspondingly provided with two toluene tail gas condensers according to the alkali washing warming kettle.
Washing portion is including washing cauldron, washing filter, washing tower 17 and washing oil reservoir storage tank 18, the upper end of washing cauldron is equipped with the feed inlet, the lower extreme of washing cauldron is equipped with the discharge gate, the lower extreme of washing filter is equipped with the feed inlet, the upper end of washing filter is equipped with the discharge gate, the washing filter includes first washing filter 15 and second washing filter 16, first washing filter 15 sets up with second washing filter 16 is parallelly connected, sets up two parallelly connected washing filters to switch the use at any time. A feed inlet is formed in the lower end of the water washing tower 17, a discharge outlet and an air outlet are formed in the upper end of the water washing tower 17, a feed inlet and an air outlet are formed in the upper end of the water washing oil layer storage tank 18, and a discharge outlet is formed in the lower end of the water washing oil layer storage tank 18; the feed inlet of washing cauldron with the discharge gate of alkaline washing knockout tower 10 is connected, the discharge gate of washing cauldron is connected with the feed inlet of washing filter, the discharge gate of washing filter is connected with the feed inlet of washing tower 17, the discharge gate of washing tower 17 is connected with the feed inlet of washing oil reservoir storage tank 18, the gas outlet of washing tower 17, the gas outlet of washing oil reservoir storage tank 18 all are connected with toluene tail gas condensation recovery unit.
The washing part further comprises a washing liquid delivery pump, the washing liquid delivery pump comprises a first washing liquid delivery pump 13 and a second washing liquid delivery pump 14, an interconnection pipeline is arranged between the first washing liquid delivery pump 13 and the second washing liquid delivery pump 14 and can be mutually switched for use, the washing kettle comprises a first washing kettle 11 and a second washing kettle 12 which are arranged in parallel, and both a gas outlet of the first washing kettle 11 and a gas outlet of the second washing kettle 12 are connected with a toluene tail gas condensation recovery device; the first washing liquid delivery pump 13 is connected with a discharge port of the first washing kettle 11, the second washing liquid delivery pump 14 is connected with a discharge port of the second washing kettle 12, and the first washing liquid delivery pump 13 and the second washing liquid delivery pump 14 are both connected with a feed port of the washing filter. The washing kettle and the washing liquid delivery pump are correspondingly arranged in two numbers so as to be switched to use at any time.
The washing portion still includes washing oil layer delivery pump 19, washing oil layer delivery pump 19 is connected with washing oil layer storage tank 18 and rising film evaporator 20 respectively, washing oil layer delivery pump 19 is located between washing oil layer storage tank 18 and rising film evaporator 20. The water-washed oil layer delivery pump 19 is used for pumping the water-washed oil layer in the water-washed oil layer storage tank 18 to the climbing film evaporator 20 for treatment.
The distillation part comprises a climbing-film evaporator 20, a climbing-film separation tank 21 and a thin-film evaporator 23, the lower end of the climbing-film evaporator 20 is provided with a feed port, the upper end of the climbing-film evaporator 20 is provided with a discharge port, the upper end of the climbing-film separation tank 21 is provided with a feed port and a gas outlet, the lower end of the climbing-film separation tank 21 is provided with a discharge port, the upper end of the thin-film evaporator 23 is provided with a feed port and a gas outlet, and the lower end of the thin-film evaporator 23 is provided with a discharge port; the feed inlet of the climbing-film evaporator 20 is connected with the discharge outlet of the water-washed oil layer storage tank 18, the discharge outlet of the climbing-film evaporator 20 is connected with the feed inlet of the climbing-film separation tank 21, the discharge outlet of the climbing-film separation tank 21 is connected with the feed inlet of the film evaporator 23, and the gas outlet of the climbing-film separation tank 21 and the gas outlet of the film evaporator 23 are both connected with a toluene tail gas condensation recovery device.
The evaporation part further comprises a film lifting and conveying pump 22, the film lifting and conveying pump 22 is respectively connected with the film lifting and separating tank 21 and the film evaporator 23, and the film lifting and conveying pump 22 is located between the film lifting and separating tank 21 and the film evaporator 23. And the membrane lifting liquid conveying pump 22 is used for pumping the materials treated by the membrane lifting separation tank 21 to the thin film evaporator 23 for treatment.
The crude product processing part comprises a refining distillation kettle 25 and a refining finished product kettle 26, wherein a feed inlet of the refining distillation kettle 25 is connected with a discharge outlet of the thin film evaporator 23, and a discharge outlet of the refining distillation kettle 25 is connected with a feed inlet of the refining finished product kettle 26.
The crude product processing part also comprises a crude product conveying pump 24, the crude product conveying pump 24 is respectively connected with the thin film evaporator 23 and the refined distillation kettle 25, and the crude product conveying pump 24 is positioned between the thin film evaporator 23 and the refined distillation kettle 25. The crude product transfer pump 24 is used for pumping the material in the thin film evaporator 23 to the refining still 25 for processing.
All the devices and components of this embodiment are correspondingly provided with accessories such as valves and control instruments, and the specific setting modes of the accessories are well known to those skilled in the art and are not described herein. The kettles, towers, pumps, tanks, condensers, filters, evaporators and the like to which the present invention relates are well known to those skilled in the art, and the internal structure thereof will not be described herein.
The process for removing sulfur and chlorine in the production of 2-ethyl anthraquinone comprises the following steps:
(1) Passing the prepared liquid caustic soda with the mass concentration of 3% through a flowmeter according to the proportion of 1m 3 The solution is pumped into an alkaline washing mixing kettle, the liquid level reaches an overflow port, an alkaline washing external circulating pump is started, and the extract (the solution of crude anthraquinone toluene) is pumped into a conveying pump and a flowmeter according to the volume of 1.5m 3 After the mixture is subjected to alkaline washing in the alkaline washing mixing kettle for 1 hour, an oil layer and waste alkaline water overflow from a discharge port at the upper end of the alkaline washing mixing kettle together to enter an alkaline washing preheating kettle; toluene tail gas generated after the materials are treated by the alkali washing mixing kettle is sent to a toluene tail gas condensation recovery device for toluene recovery.
(2) Preheating and alkali washing: transferring the material subjected to mixed alkali washing into a preheating alkali washing kettle, recovering waste heat steam, heating the alkali washing preheating kettle to 75 ℃ through a jacket, wherein the waste heat steam is the hot steam recovered from a chlorobenzene distillation system and a toluene distillation system, and stirring to remove impurities; after 0.5h in the alkali washing preheating kettle, the oil layer and the waste alkali water are transferred out to the first alkali washing heating kettle or the second alkali washing heating kettle through a discharge hole at the lower end of the alkali washing preheating kettle; and (4) sending condensed water generated in the process of preheating and alkali washing to a hot water tank.
(3) Heating and alkali washing: feeding the preheated alkali-washed material into an alkali-washing warming kettle for warming and alkali-washing, recovering waste heat steam, heating the alkali-washing warming kettle to 105 ℃ through a jacket, starting stirring, performing alkali-washing for 1 hour, and pumping into an alkali-washing separation tower; the resulting condensate is directed to a hot water tank. Meanwhile, the toluene tail gas generated by the alkali washing warming kettle treatment is output to a first toluene tail gas condenser or a second xylene tail gas condenser from a gas outlet of the first alkali washing warming kettle or a gas outlet of the second alkali washing warming kettle, the toluene tail gas condenser performs circulating cooling treatment by utilizing circulating water which enters from bottom to top, and the toluene tail gas is sent to a toluene tail gas condensation and recovery device for toluene recovery.
(4) Oil-water separation: and (3) pumping the material treated by the alkali washing warming kettle to a lower end feed inlet of an alkali washing separation tower by a first alkali washing warming kettle circulating pump or a second alkali washing warming kettle circulating pump, treating the material in the alkali washing separation tower by means of different density differences of the material and design of a U-shaped pipe, automatically discharging the material in a layering manner in the alkali washing separation tower, discharging oil from the upper part of the tower, discharging alkaline waste water from the bottom of the tower, and recycling the alkaline waste water to an alkaline waste water tank.
(5) Washing an oil layer with water: transferring the oil layer obtained in the step (4) into a first washing kettle or a second washing kettle for stirring and washing, and then standing for layering; the used water of washing is the industrial water that adds by the top of washing cauldron, and the water layer after the layering of stewing is separated out by the cauldron bottom of washing cauldron, and waste water goes to the alkali waste water groove and carries out recycle, and remaining oil reservoir is sent to first washing filter or second washing filter by first washing liquid delivery pump or second washing liquid delivery pump. In the process, the toluene tail gas generated in the first water washing kettle or the second water washing kettle is sent to a toluene tail gas condensation recovery device for toluene recovery.
(6) Filtering an oil layer: transferring the oil layer in the water washing kettle to a water washing filter, and filtering to remove impurities by using high-precision filter cloth;
(7) Washing and layering: and (3) enabling the oil layer obtained by filtering and impurity removing in the step (6) to enter a feeding hole at the lower end of a washing tower, adding hot water from the middle upper part of the washing tower, enabling the two phases to be in countercurrent contact, automatically discharging materials in a layered mode by means of different density differences of the materials and design of a U-shaped pipe, discharging the wastewater from a discharging hole at the upper part of the washing tower through an oil outlet layer, discharging the wastewater from a water outlet at the bottom of the washing tower, enabling the wastewater to go to an alkali waste water tank, and enabling the toluene tail gas generated in the washing tower to go to a toluene tail gas condensation recovery device for toluene recovery.
(8) Solvent distillation: the oil layer obtained by the treatment in the step (7) enters a water-washed oil layer storage tank, then is pumped into a climbing film evaporator by a water-washed oil layer conveying pump, 90% of extractant toluene is distilled out at normal pressure by heating (111-115 ℃) through the climbing film evaporator, the treated material is transferred into a climbing film separation tank for treatment, and is pumped into a film evaporator by a climbing film liquid conveying pump after being treated for heating and pressure reduction (100-130 ℃), -85 KPa) to distill out the remaining 10% of extractant toluene, so that a 2-ethyl anthraquinone crude product is obtained; in the process, toluene tail gas generated in the water-washed oil layer storage tank, the climbing film separation tank and the film evaporator is sent to a toluene tail gas condensation recovery device for toluene recovery.
(9) And (3) refining a product: transferring a molten 2-ethyl anthraquinone crude product into a refined distillation kettle from a film evaporator through a crude product transfer pump, grinding flake caustic soda into powder and adding the powder into the refined distillation kettle, wherein 550Kg of the 2-ethyl anthraquinone crude product transferred into the refined distillation kettle is correspondingly added with 0.6Kg of the powder caustic soda, the powder caustic soda is added into the refined distillation kettle three times in the process of feeding the 2-ethyl anthraquinone crude product, the adding amount is the same every time, namely 0.2Kg is added every time, the refined distillation kettle is added once when feeding to 1/3 of the liquid level, the refined distillation kettle is added once when feeding to 1/2 of the liquid level, the refined distillation kettle is added once when feeding is finished, stirring is uniform, and the distillation is carried out for 12 hours at high temperature and reduced pressure (200-230 ℃ and less than 100 Pa) to complete the processes of sulfur and chlorine removal in the production of 2-ethyl anthraquinone, transferring the 2-ethyl anthraquinone finished product into a refined product kettle, slicing and packaging the finished product as required, and conveying the finished product into a vacuum pumping system of tail gas generated at the top gas outlet of the refined product kettle.
Example 2
The process for removing sulfur and chlorine in the production of 2-ethyl anthraquinone comprises the following steps:
(1) Mixed alkali washing: 1m of liquid alkali with the mass concentration of 1 percent 3 H adding the extract liquid to be removed of sulfur and chlorine to 1.5m 3 Adding the mixture into the reactor for mixed alkaline washing, wherein the mixed alkaline washing time is 1h;
(2) Preheating and alkali washing: carrying out preheating alkali washing on the material subjected to mixed alkali washing, and stirring to remove impurities, wherein the preheating alkali washing temperature is 70 ℃, and the preheating alkali washing time is 1h;
(3) Heating and alkali washing: heating and alkali washing the material subjected to the pre-heating alkali washing, wherein the heating and alkali washing temperature is 100 ℃, and the heating and alkali washing time is 1h;
(4) Oil-water separation: performing oil-water separation on the material subjected to temperature-rising alkali washing, and removing a water layer and an oil layer;
(5) Washing an oil layer with water: stirring and washing the oil layer obtained in the step (4), standing for layering, removing a water layer, and taking the oil layer;
(6) Filtering an oil layer: filtering the oil layer obtained in the step (5) to remove impurities;
(7) Washing and layering: the oil layer obtained by the treatment in the step (6) enters the middle lower part of a washing tower, hot water is added from the middle upper part of the washing tower, two phases are in countercurrent contact, the materials are automatically discharged in a layered manner by means of different density differences of the materials and the design of a U-shaped pipe, an oil layer is formed at the upper part of the tower, and wastewater is discharged from the lower part of the tower;
(8) Solvent distillation: heating the oil layer obtained by the treatment in the step (7) at normal pressure to distill most of the extractant toluene, heating at reduced pressure to distill the residual extractant toluene to obtain a crude product of 2-ethyl anthraquinone;
(9) And (3) refining a product: transferring the 2-ethyl anthraquinone crude product into a refining distillation kettle, grinding flake caustic soda into powder, adding the powder caustic soda three times in the process of feeding the 2-ethyl anthraquinone crude product into the refining distillation kettle, wherein 600Kg of the 2-ethyl anthraquinone crude product is fed into the refining distillation kettle, the amount of the added powder caustic soda is totally 0.8Kg, the adding is carried out once when the feeding of the refining distillation kettle reaches 1/3 liquid level, the adding is carried out once when the feeding of the refining distillation kettle reaches 1/2 liquid level, the adding is carried out once when the feeding of the refining distillation kettle is finished, the amount of the added powder caustic soda is the same each time, the stirring is uniform, and the distillation is carried out for 12 hours under high temperature and reduced pressure (200-230 ℃ and less than 100 Pa), so that the processes of sulfur removal and chlorine removal in the production of 2-ethyl anthraquinone are completed.
Example 3
The process for removing sulfur and chlorine in the production of 2-ethyl anthraquinone comprises the following steps:
(1) Mixed alkali washing: carrying out mixed alkaline washing on liquid caustic soda with the mass concentration of 5% and the extraction liquid of the sulfur and the chlorine to be removed, wherein the mixed alkaline washing time is 1.5h;
(2) Preheating and alkali washing: carrying out preheating alkali washing on the material subjected to mixed alkali washing, and stirring to remove impurities, wherein the preheating alkali washing temperature is 80 ℃, and the preheating alkali washing time is 0.5h;
(3) Heating and alkali washing: heating and alkali washing the material subjected to the pre-heating alkali washing, wherein the heating and alkali washing temperature is 110 ℃, and the heating and alkali washing time is 0.5h;
(4) Oil-water separation: carrying out oil-water separation on the material subjected to temperature-rising alkali washing, removing a water layer and taking an oil layer;
(5) Washing an oil layer with water: stirring and washing the oil layer obtained in the step (4), standing for layering, removing a water layer, and taking the oil layer;
(6) Filtering an oil layer: filtering the oil layer obtained in the step (5) to remove impurities;
(7) Washing and layering: the oil layer obtained by the treatment in the step (6) enters the middle lower part of a washing tower, hot water is added from the middle upper part of the washing tower, the two phases are in countercurrent contact, the materials are automatically discharged in a layered mode by means of different density differences of the materials and design of a U-shaped pipe, the oil layer is formed in the upper part of the tower, and waste water is discharged from the lower part of the tower;
(8) Solvent distillation: heating the oil layer obtained by the treatment in the step (7) at normal pressure to distill most of the extractant toluene, heating at reduced pressure to distill the residual extractant toluene to obtain a crude product of 2-ethyl anthraquinone;
(9) And (3) refining a product: transferring the 2-ethyl anthraquinone crude product into a refining distillation kettle, grinding flake caustic soda into powder, adding the powder caustic soda into the refining distillation kettle in the process of feeding the 2-ethyl anthraquinone crude product, wherein 700Kg of the 2-ethyl anthraquinone crude product is fed into the refining distillation kettle, the amount of the added powder caustic soda is 1Kg in total, the powder caustic soda is added in three times, the amount of the added powder caustic soda is the same each time, the refining distillation kettle is fed to 1/3 liquid level, the refining distillation kettle is fed to 1/2 liquid level once, the refining distillation kettle is fed once when the feeding is finished, the refining distillation kettle is stirred uniformly, and the refining distillation kettle is subjected to high-temperature reduced pressure distillation (200-230 ℃ and less than 100 Pa) for 13 hours to complete the processes of sulfur removal and chlorine removal in the production of 2-ethyl anthraquinone.
Comparative example 1
The process for removing sulfur and chlorine in the production of 2-ethylanthraquinone is basically the same as that of example 1, except that: the preheating alkali washing in the step (2) is omitted, the temperature is directly raised to 105 ℃ after the mixed alkali washing, and the temperature-raising alkali washing time is 1.5h.
Comparative example 2
The process for removing sulfur and chlorine in the production of 2-ethylanthraquinone is basically the same as that of example 1, except that: and (4) saving the heating alkali washing in the step (3), after mixed alkali washing, heating to 75 ℃ for preheating alkali washing, wherein the preheating alkali washing time is 1.5h, and thus the alkali washing process is completed.
Comparative example 3
The process for removing sulfur and chlorine in the production of 2-ethylanthraquinone is basically the same as that of example 1, except that: and (3) in the alkali washing operation of the steps (1) to (3), the used alkali washing temperature is 85-90 ℃, and the alkali washing process is completed.
Comparative example 4
The process for removing sulfur and chlorine in the production of 2-ethylanthraquinone is basically the same as that of example 1, except that: and (4) adding no soda powder into the product refining in the step (9).
Comparative example 5
The process for removing sulfur and chlorine in the production of 2-ethylanthraquinone is basically the same as that of example 1, except that: in the product refining of the step (9), all the caustic soda powder is added at one time when the refined distillation kettle is fed to 1/3 of the liquid level.
The untreated extract from example 1, the alkaline washed extract from steps (1) to (3) of example 1, the alkaline washed extract from comparative example 2, the alkaline washed extract from comparative example 3, the finished product from example 1, the finished product from comparative example 4, and the finished product from comparative example 5 were taken for analysis, and the specific data are shown in table 1 below:
TABLE 1
| Group of | Crude anthraquinone content (%) | Sulfur content (ppm) | Chlorine content (ppm) |
| Untreated extract | 98.84 | 1535 | 1752 |
| Example 1 extract after alkali washing | 98.90 | 23 | 31 |
| Comparative example 1 alkali-washed extract solution | 98.92 | 51 | 63 |
| Comparative example 2 alkali-washed extract | 98.88 | 183 | 201 |
| Comparative example 3 alkali-washed extract | 98.89 | 95 | 143 |
| Example 1 finished product | 98.85 | 1.99 | 3.39 |
| Finished product of comparative example 4 | 98.89 | 12 | 14 |
| Finished product of comparative example 5 | 98.87 | 7.62 | 9.91 |
As can be seen from the comparison of the data in the table 1, the alkaline cleaning process of preheating alkaline cleaning and then heating alkaline cleaning provided by the invention has very obvious effects of removing sulfur and chlorine in the production of 2-ethylanthraquinone, under the conditions, after the effects of sulfur and chlorine removal are achieved, powdered alkali is added during refining, the sulfur and chlorine in the finished product of 2-ethylanthraquinone can be controlled to be lower than the national standard requirements, the content is extremely low, and the production requirement of hydrogen peroxide is better met. In addition, the time and the step of adding the powdered alkali have certain influence on the sulfur and chlorine removal effect of the finished product, and the sulfur and chlorine removal effect of the finished product can be obviously improved by adding the powdered alkali three times at different times.
Although the present invention has been described with respect to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
- The process for removing sulfur and chlorine in the production of 2-ethyl anthraquinone is characterized by comprising the following steps:(1) Mixed alkali washing: carrying out mixed alkaline washing on the liquid caustic soda with the mass concentration of 1-5% and the extract liquor to be subjected to sulfur and chlorine removal, wherein the mixed alkaline washing time is 1-1.5 h;(2) Preheating and alkali washing: carrying out preheating alkali washing on the material subjected to mixed alkali washing, and stirring to remove impurities, wherein the preheating alkali washing temperature is 70-80 ℃, and the preheating alkali washing time is 0.5-1 h;(3) Heating and alkali washing: heating and alkali washing the material subjected to the preheating and alkali washing, wherein the heating and alkali washing temperature is 100-110 ℃, and the heating and alkali washing time is 0.5-1 h;in the step (2) and the step (3), the heating process of preheating alkali washing and heating alkali washing is heating by using waste heat steam, wherein the waste heat steam refers to heat steam recovered from a chlorobenzene distillation system and a toluene distillation system;(4) Oil-water demixing: performing oil-water separation on the material subjected to temperature-rising alkali washing, and removing a water layer and an oil layer;(5) Washing an oil layer with water: stirring and washing the oil layer obtained in the step (4), standing for layering, removing a water layer, and taking the oil layer;(6) Filtering an oil layer: filtering the oil layer obtained in the step (5) to remove impurities;(7) Washing and layering: the oil layer obtained by the treatment in the step (6) enters the middle lower part of a washing tower, hot water is added from the middle upper part of the washing tower, the two phases are in countercurrent contact, the materials are automatically discharged in a layered mode by means of different density differences of the materials and design of a U-shaped pipe, the oil layer is formed in the upper part of the tower, and waste water is discharged from the lower part of the tower;(8) Solvent distillation: heating the oil layer obtained by the treatment in the step (7) at normal pressure to distill most of the extractant toluene, heating at reduced pressure to distill the residual extractant toluene to obtain a crude product of 2-ethyl anthraquinone;(9) And (3) refining a product: transferring the 2-ethyl anthraquinone crude product into a refining distillation still, grinding flake caustic soda into powder, adding the powder caustic soda into the refining distillation still for three times during the process of feeding the 2-ethyl anthraquinone crude product, uniformly stirring, and carrying out high-temperature reduced pressure distillation to complete the processes of sulfur removal and chlorine removal in the production of 2-ethyl anthraquinone.
- 2. The process for the removal of sulfur and chlorine in the production of 2-ethylanthraquinone according to claim 1, characterized in that: in the step (8), the heating atmospheric distillation is carried out under the conditions of 111-115 ℃ and normal pressure; the heating reduced pressure distillation is carried out under the conditions of 100-130 ℃ and-85 KPa.
- 3. The process for the removal of sulfur and chlorine in the production of 2-ethylanthraquinone according to claim 1, characterized in that: in the step (9), the high-temperature reduced-pressure distillation is carried out under the conditions of 200-230 ℃ and less than 100Pa, and the high-temperature reduced-pressure distillation time is 12-13h.
- 4. The process for the removal of sulfur and chlorine in the production of 2-ethylanthraquinone according to claim 1, characterized in that: in the step (9), the addition amount of the powder alkali is 1.0-1.5Kg of powder alkali added to each ton of the crude 2-ethyl anthraquinone product.
- 5. The process for the removal of sulfur and chlorine in the production of 2-ethylanthraquinone according to claim 1, characterized in that: in the step (9), the caustic soda powder is added into the refined distillation still for three times, the addition amount is the same every time, the addition is carried out once when the refined distillation still is fed to 1/3 of the liquid level, the addition is carried out once when the refined distillation still is fed to 1/2 of the liquid level, and the addition is carried out once when the refined distillation still is fed.
- 6. The process for the removal of sulfur and chlorine in the production of 2-ethylanthraquinone according to claim 1, characterized in that: the sulfur and chlorine removal process is carried out in a sulfur and chlorine removal system in the production of 2-ethylanthraquinone, and the sulfur and chlorine removal system in the production of 2-ethylanthraquinone comprises an alkali washing part, a water washing part, a distillation part and a crude product treatment part:the alkaline washing part comprises an alkaline washing mixing kettle, an alkaline washing preheating kettle, an alkaline washing warming kettle and an alkaline washing separation tower, wherein a discharge hole of the alkaline washing mixing kettle is connected with a feed hole of the alkaline washing preheating kettle, a discharge hole of the alkaline washing preheating kettle is connected with a feed hole of the alkaline washing warming kettle, and a discharge hole of the alkaline washing warming kettle is connected with a feed hole of the alkaline washing separation tower;the washing part comprises a washing kettle, a washing filter, a washing tower and a washing oil layer storage tank, wherein a feeding port of the washing kettle is connected with a discharging port of the alkaline washing separation tower, a discharging port of the washing kettle is connected with a feeding port of the washing filter, a discharging port of the washing filter is connected with a feeding port of the washing tower, and a discharging port of the washing tower is connected with a feeding port of the washing oil layer storage tank;the distillation part comprises a climbing-film evaporator, a climbing-film separation tank and a thin-film evaporator, a feed port of the climbing-film evaporator is connected with a discharge port of the water-washed oil layer storage tank, a discharge port of the climbing-film evaporator is connected with a feed port of the climbing-film separation tank, and a discharge port of the climbing-film separation tank is connected with a feed port of the thin-film evaporator;the crude product treatment part comprises a refined distillation still and a refined finished product kettle, a feed inlet of the refined distillation still is connected with a discharge outlet of the thin film evaporator, and a discharge outlet of the refined distillation still is connected with a feed inlet of the refined finished product kettle;the process steps of adopting the sulfur and chlorine removal system in the 2-ethyl anthraquinone production to remove sulfur and chlorine are as follows: transferring the extract liquor and the liquid caustic soda to be subjected to sulfur and chlorine removal into an alkaline washing mixing kettle for mixed alkaline washing; after the materials are treated by an alkali washing mixing kettle, transferring the materials to an alkali washing preheating kettle for preheating alkali washing; transferring the material treated by the alkali washing preheating kettle to an alkali washing temperature rising kettle for heating and alkali washing, transferring the material treated by the alkali washing temperature rising kettle to an alkali washing separation tower for oil-water separation, transferring an oil layer obtained after the treatment of the alkali washing separation tower to a water washing kettle for water washing, transferring the oil layer obtained after the water washing to a water washing filter for filtration, transferring the oil layer obtained after the filtration to a water washing tower for water washing, transferring the obtained oil layer to a water washing oil layer storage tank, transferring the oil layer to a climbing film evaporator for heating and atmospheric distillation treatment, transferring the treated material to a climbing film separation tank for treatment, transferring the treated material to a film evaporator for heating and reduced pressure distillation, and obtaining the productTo obtain a 2-ethyl anthraquinone crude product; transferring the 2-ethyl anthraquinone crude product into a refining distillation kettle for refining, transferring into a refined product kettle for storage,the processes of sulfur removal and chlorine removal are completed.
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