CN110755991B - Styrene waste gas treatment method - Google Patents
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Abstract
A styrene waste gas treatment method belongs to the technical field of treatment of organic pollutants in waste gas. The method is characterized by comprising the following processing steps: soaking the carbon fiber in butanol solution containing TMPOP and phosphoric acid or phosphate, and heating and activating to obtain modified activated carbon fiber; loading the modified activated carbon fiber into an adsorber of an adsorption device; the tail gas after the styrene-containing gas is adsorbed flows out of the bed layer, and the adsorption device which finishes the adsorption is desorbed; condensing and separating organic mixed steam generated by desorption; adding a polymerization inhibitor into the separated styrene, and overflowing and recovering the styrene. The invention can inhibit the polymerization of styrene in the desorption process, and has high desorption efficiency and long service life of the activated carbon fiber.
Description
Technical Field
A styrene waste gas treatment method belongs to the technical field of treatment of organic pollutants in waste gas.
Background
The styrene monomer is active in chemical property, is an important polymerized monomer, can be polymerized by itself or with other monomers, and is widely applied to the fields of synthetic high polymer materials, coatings, medicines and the like. Styrene can undergo a slow thermally-activated polymerization at ambient temperature. In the exhaust gas treatment, styrene belongs to volatile organic compounds and malodorous gases. Volatile organic compounds (VOCs for short) are a large class of organic waste gases, and generally refer to organic compounds with saturated vapor pressure of more than 70Pa at normal temperature and boiling point of less than 260 ℃ at normal pressure. Mainly comprises hydrocarbons, benzene and derivatives thereof, phenol and derivatives thereofDerivatives, alcohols, aldehydes, ketones, and the like. Styrene belongs to typical monocyclic aromatic VOCs, and generates toxicity and carcinogenicity to human mucosa, liver, kidney, lung and nervous system through respiration. The emission standard GB 31571-2015 of the pollutants for the petrochemical industry, which is implemented from 7.1.2017, clearly limits that the emission concentration of the styrene does not exceed 50mg/m3。
In the processes of production, storage and loading of styrene, along with the rise of the liquid level of a product storage tank, the volume of a gas space is gradually reduced, oil gas is gradually discharged, factors such as process equipment and the like are added, the condition of external leakage of waste gas also exists in actual operation, the content of styrene in the tail gas of loading and the direct exhaust of a production device can not reach the discharge standard specified by the state, the styrene needs to be recycled, and the problem of environment pollution caused by waste gas is fundamentally solved.
The common treatment methods for volatile organic compounds include absorption, adsorption, condensation, combustion and membrane separation methods, and the methods for recovering valuable organic compounds in the waste gas generally adopt condensation, adsorption, membrane separation methods or a combination method thereof and the like. With the strictness of the national environmental protection regulations, the activated carbon adsorption method becomes a research hotspot of scholars at home and abroad in recent years, and the difficulty for treating the styrene waste gas is how to solve the problem of polymerization in the treatment process.
Chinese patent CN200310101839.6 discloses a device and method for treating organic waste gas by adsorption recovery of activated carbon fiber, which is characterized in that the recovery device comprises a rectification recovery system for recovering organic solvent therein, the system comprises a rectification column between a desorption gas outlet and a condenser and a solvent receiving tank behind the condenser; and also comprises a desorption gas bypass cooling system. The extracorporeal circulation cooling and dehumidification treatment is carried out on the resolved adsorber, so that the adsorption effect of the adsorber in a high-temperature adsorption stage is improved, and the adsorption capacity is increased. The organic pollutants comprise benzene, toluene, acetone, cyclohexane and the like, but the treatment of waste gas of easily polymerized styrene is not involved.
Chinese patent CN201210062479.2 describes a device for continuously adsorbing and desorbing organic waste gas by using activated carbon, which comprises an adsorption tower, a desorption tower, an activated carbon fluidization system and an organic solvent recovery system, wherein the activated carbon is used for continuously adsorbing and treating organic waste gas containing dichloromethane, toluene, xylene, benzene and the like, and continuously desorbing the organic solvent. The organic waste gas and the active carbon are in reverse contact, the gas distribution is uniform, and the particle fluidity is good. The active carbon is recycled by adopting a pneumatic conveying mode. The invention is characterized in that the device is improved, the labor intensity of staff is greatly reduced, the pollution of powdered activated carbon to the environment is greatly reduced, the conventional organic pollutants with lower boiling points are treated, and the problems of styrene waste gas treatment and how to avoid polymerization influence adsorption in the treatment process are not disclosed.
Chinese patent CN 01137385.7 discloses a continuous preparation method of activated carbon fiber felt and cloth, which is obtained by drying fibril (intermediate) after passing through a preprocessor filled with 2% ammonium phosphate solution at a constant speed, then carbonizing at 300-450 ℃, and finally activating at 850-1300 ℃ under the condition of mixed gas of nitrogen and water vapor. The product has a specific surface area of 800-3200 m2/g and a pore size distribution of 0.6-2.3 nm. Good appearance and hand feeling, little ash, no spot, suitability for being used as an adsorbent in various waste water and waste gas treatment and purification devices, large adsorption capacity, high removal speed, easy regeneration, heat resistance, acid and alkali resistance. The patent does not relate to the use effect of the activated carbon fiber.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art, and provides a styrene waste gas treatment method which increases the specific surface area of the used adsorbent and has polymerization inhibition performance.
The technical scheme adopted by the invention for solving the technical problems is as follows: the styrene waste gas treatment method is characterized by comprising the following treatment steps:
1) soaking the carbon fiber in a butanol solution containing TMPOP and phosphoric acid or phosphate, wherein the mass ratio of the TMPOP to the phosphoric acid or the phosphate is 0.18-6: 1, the total mass concentration of the TMPOP and the phosphoric acid or the phosphate is 1-10%, the soaking time is 10-36 h, filtering the solution, heating and activating in inert gas at the temperature of 105-170 ℃, and cooling to obtain the modified activated carbon fiber;
2) loading the modified activated carbon fiber into an adsorber of an adsorption device; the adsorption device comprises 3 adsorbers, and switching operation of one adsorption state, one drying state and one adsorption saturation state is always kept; the method comprises the following steps that styrene-containing gas firstly enters an adsorber in an adsorption state for adsorption, styrene is adsorbed on the surface of activated carbon fibers, tail gas after adsorption flows out of a bed layer, dry air is supplemented and then the tail gas is sent into the adsorber in a dry state for cooling and drying and secondary adsorption, low-pressure steam enters the adsorber in an adsorption saturated state while adsorption is carried out, and the adsorber after adsorption is desorbed;
3) condensing the organic mixed steam generated by desorption in a condenser, and then carrying out liquid-liquid separation in a separator, wherein the upper layer liquid is styrene, and the lower layer liquid is water; 10-30 ppm of polymerization inhibitor is added into the separated styrene, and the styrene overflows and is recovered.
The invention aims to solve the technical problem of providing a styrene waste gas treatment method, which is characterized in that activated carbon fibers are modified by soaking the carbon fibers in a butanol solution containing tris (2, 2,6, 6-tetramethyl-4-hydroxy-piperidinyloxy) phosphine (TMPOP) and phosphoric acid or phosphate, so that the activated carbon fibers have polymerization inhibition performance while the specific surface is increased, the adsorption efficiency is improved, the activated carbon fibers can be quickly and effectively subjected to desorption regeneration, the polymerization of styrene is avoided in the regeneration process, the problems that the adsorption and desorption rate is low, the styrene is easy to polymerize in the desorption process, the service life of the activated carbon fibers is short, the styrene is difficult to reach the emission standard after adsorption in the conventional styrene adsorption technology are solved, and the use efficiency of the activated carbon fibers is improved. The invention uses TMPOP and phosphoric acid or phosphate to compound and modify the carbon fiber, the TMPOP is used as a polymerization inhibitor and an activator, the fiber is activated in the modification process, the carbon skeleton is repeatedly beaten, a large amount of pore structures are created, the specific surface is enlarged, the active carbon fiber is endowed with stronger adsorption force, the polymerization inhibition performance is increased, the polymerization of styrene in the desorption process is inhibited, the desorption efficiency is high, the service life of the active carbon fiber is long, and the problem of low styrene absorption and desorption efficiency is fundamentally solved.
Preferably, the total concentration of the TMPOP and the phosphoric acid or the phosphate in the butanol in the step 1) is 2-6%. The carbon fiber is modified by the preferred total mass concentration to form a finer pore structure, so that the specific surface of the carbon fiber achieves the maximum effect of the invention, and simultaneously, the stronger adsorption force and the high temperature resistance of the activated carbon fiber achieve the best performance. The TMPOP has better polymerization inhibition performance and high temperature resistance, belongs to a high-temperature polymerization inhibitor and is used as an activator of carbon fiber,
the phosphate is preferably a hydrogen phosphate salt, including monohydrogen phosphate and dihydrogen phosphate. Preferably, the phosphate in step 1) is sodium dihydrogen phosphate, potassium dihydrogen phosphate and/or ammonium dihydrogen phosphate. The carbon fiber is modified by the preferred phosphate to form a finer pore structure, so that the specific surface of the carbon fiber is larger, and the activated carbon fiber has stronger adsorption force and better polymerization inhibition performance.
Preferably, the mass ratio of the TMPOP to the phosphoric acid or the phosphate in the step 1) is 0.25-5: 1. The preferable mass ratio is modified with carbon fiber to form a finer pore structure, so that the specific surface is larger, and the active carbon fiber has stronger adsorption force and better polymerization inhibition performance.
Preferably, the mass ratio of the TMPOP to the phosphoric acid or the phosphate in the step 1) is 0.6-3: 1. The more preferable quality ratio is modified with carbon fiber to form a finer pore structure, so that the specific surface of the carbon fiber can achieve the maximum effect of the invention, and simultaneously, the stronger adsorption force and the polymerization inhibition performance of the activated carbon fiber can achieve the best.
Preferably, the dipping temperature in the step 1) is 20-85 ℃, and the dipping time is 12-24 h. In the dipping process, the dipping can be carried out at normal temperature or heating, and the preferable temperature is 20-85 ℃, and the most preferable temperature is 35-65 ℃. The dipping time is preferably 12 to 24 hours. The purpose of impregnation is to form a certain amount of active functional groups on the surface of the carbon fiber, enhance the adsorption force of the carbon fiber and endow the carbon fiber with polymerization inhibition performance. After the impregnation is finished, filtering, and activating in a nitrogen or argon environment, wherein the activating temperature is preferably 120-180 ℃. In the heating process, under the action of an activating agent compounded by TMPOP and phosphoric acid or phosphate, carbon and hydrogen in raw material carbon fibers can be selectively removed, the fibers are carbonized, and carbon skeletons are rearranged to generate a large number of pore structures, so that the specific surface of the raw material carbon fibers is enlarged, and meanwhile, functional groups with polymerization inhibiting performance are formed on the surface of the raw material carbon fibers, and the activated carbon fibers with polymerization inhibiting effect are obtained.
In step 2), filling activated carbon fibers into an adsorber, switching the adsorption of styrene waste gas in 3 adsorbers, allowing the styrene waste gas to enter the adsorber in an adsorption state from the bottom, adsorbing the styrene gas by the activated carbon fibers, and allowing the styrene gas to flow out from the top of an adsorption bed layer, wherein the separation of organic components in the waste gas from air is an important characteristic of the activated carbon fiber adsorber, and the styrene concentration at an outlet of the adsorber is reduced to a lower state by the adsorption of the adsorber bed layer and is basically and completely adsorbed. The outer layer of the adsorber is provided with a jacket, and the jacket is internally communicated with circulating condensate water for taking away adsorption heat, so that the phenomenon of adsorption heat accumulation is avoided, and the effect of improving the adsorption rate is achieved.
The gas coming out of the top of the adsorber in the adsorption state is mixed with air to form enough gas volume, and the gas is used as a dry gas source to enter the adsorption bed after desorption is completed, and the exhaust steam of low-pressure steam is blown out to play a role in cooling; meanwhile, for the styrene waste gas, the styrene which is not completely adsorbed by the adsorber in the adsorption state can be adsorbed for the second time, and the content of the styrene in the tail gas after adsorption can be ensured to be lower than the national emission requirement through the process. Preferably, the volume ratio of the styrene-containing gas in the step 2) to the supplementary dry air is 1-6: 1.
when a bed of activated carbon fibers reaches a certain saturation level, regeneration is required to restore its adsorption capacity. Because the adsorption process is a reversible process, the regeneration of the activated carbon fiber can be realized by changing the adsorption equilibrium, i.e. organic substances are desorbed by introducing steam. The main functions of the introduced steam are as follows: firstly, the temperature of a bed layer can be increased by steam, and as the adsorption is physical adsorption, the temperature is increased, the adsorption quantity is reduced, and adsorbate can be desorbed; secondly, water vapor is introduced, so that the partial pressure of organic matter vapor on the surface of the adsorbent can be reduced, and when the partial pressure is lower than the saturation pressure, organic matter molecules are desorbed from the surface of the adsorbent and enter a gas phase, so that the aim of desorption is fulfilled; the steam has the function of purging, the partial pressure of organic molecules is continuously reduced through continuous purging, and the desorbed organic gas is blown out of the bed layer, so that the organic gas is continuously desorbed, and the adsorbent is regenerated.
The invention adopts low-pressure steam to desorb styrene, and the carbon fiber contains polymerization inhibitor, thereby effectively avoiding the polymerization of styrene in the desorption process and having good desorption effect.
In the step 3), after the styrene is desorbed by the steam, the mixed steam containing the styrene enters a condenser for condensation, and the cooling medium is cooling water. When the boiling point of styrene is lower than the temperature of the cooling water, it can be condensed. The temperature of the oil-water mixture can be reduced to below 35 ℃ by cooling through a condenser. The oil-water mixture condensed enters an oil-water separator to fully separate the styrene from the water.
Adding polymerization inhibitor into the upper layer liquid styrene, wherein the polymerization inhibitor can be tert-butyl catechol (TBC), 2, 5-ditert amyl hydroquinone, p-hydroxyanisole, hydroxylamine compounds such as dihydroxypropyl hydroxylamine (HPHA), aniline compounds such as N, N' -diisobutyl hydroquinone, phenol compounds such as Hydroquinone (HQ), 2,3, 5-trimethyl-4-nitrosophenol, p-tert-butyl catechol (TBC), 2, 5-ditert amyl hydroquinone (DTBHQ), 2, 6-dibutyl-4-methylphenol and the like, quinone compounds such as benzoquinone, tert-butyl benzoquinone (TBBQ), benzoquinone diimide and 1, 4-naphthoquinone, and one or more of the polymerization inhibitors can be compounded and applied to the recovered styrene. Preferably, the polymerization inhibitor in the step 3) is a storage type polymerization inhibitor TBC, HQ, hydroxylamine compound or a compound of two of the storage type polymerization inhibitors TBC, HQ and hydroxylamine compound. The preferable polymerization inhibitor can achieve better polymerization inhibition effect with smaller dosage, and the dosage is 10-15 ppm.
Compared with the prior art, the invention has the beneficial effects that: the styrene waste gas treatment method is different from the adsorption and process effects of the activated carbon fiber in the prior art, the TMPOP and phosphoric acid or phosphate compound formula with dual functions of activation and polymerization inhibition is adopted in the activation process of the carbon fiber, the specific surface is increased through impregnation and fiber activation, and the polymerization inhibition performance is improved while the activated carbon fiber is endowed with stronger adsorption force; two-stage adsorption is adopted, wherein the first stage adopts jacket internal circulation cooling for taking away adsorption heat in time, thereby effectively improving the recovery rate of styrene and eliminating the phenomenon of adsorption heat accumulation; the second adsorption plays a role in cooling; meanwhile, the polymerization phenomenon of styrene in the desorption process is effectively avoided, the service life of the activated carbon fiber is prolonged, and the content of styrene in the tail gas after adsorption is lower than the national emission requirement. The whole process operation has the characteristics of high adsorption and desorption efficiency, safety and reliability, and realizes the safe adsorption of the easily polymerized styrene waste gas.
Detailed Description
The invention is further illustrated by the following specific examples, of which example 1 is the best mode of practice. The different activators used in the examples and comparative examples are shown in table 1. The styrene exhaust gas pollution treatment procedures of examples and comparative examples are as follows.
Example 1
1) Putting activated carbon fibers sold in a T1300 series in a container, taking butanol as a solvent, preparing TMPOP and phosphoric acid or phosphate into an activating solution, uniformly stirring, adding into a glass container, immersing the carbon fibers by about 1 cm in the activating solution at 60 ℃ for 12h, taking out, filtering, drying in the sun, and drying in an oven at 92 ℃ to achieve constant weight; placing the carbon fiber in a muffle furnace, and heating the carbon fiber in a nitrogen environment at 140 ℃ for 60 minutes to obtain modified activated carbon fiber;
2) loading the modified activated carbon fiber into an adsorber of an adsorption device; the adsorption device comprises 3 adsorbers, and switching operation of one adsorption state, one drying state and one adsorption saturation state is always kept; the styrene-containing gas firstly enters an adsorber in an adsorption state for adsorption, the styrene is adsorbed on the surface of the activated carbon fiber, the tail gas after adsorption flows out of a bed layer, dry air is supplemented and then the tail gas is sent into the adsorber in a dry state, and the volume ratio of the styrene-containing gas to the supplemented dry air is 2.5: 1, cooling and drying, and performing secondary adsorption, wherein low-pressure steam enters an adsorber in an adsorption saturated state while adsorption is performed, and the adsorber which finishes adsorption is desorbed;
3) condensing the organic mixed steam generated by desorption in a condenser, and then carrying out liquid-liquid separation in a separator, wherein the upper layer liquid is styrene, and the lower layer liquid is water; 10ppm of polymerization inhibitor is added into the separated styrene, the polymerization inhibitor is a compound polymerization inhibitor of TBC and HQ according to the mass ratio of 1:1, and the styrene overflows and is recovered.
Example 2
1) Putting activated carbon fibers with a commercial model of T1300 series into a container, using butanol as a solvent, preparing TMPOP and phosphoric acid or phosphate into an activating solution, uniformly stirring, adding into a glass container, wherein the activating solution submerges the carbon fibers by about 1 cm, the soaking temperature is 40 ℃, the soaking time is 18h, taking out, filtering, drying in the sun, and then drying in an oven at 93 ℃ to constant weight; then placing the carbon fiber in a muffle furnace, heating the carbon fiber in a nitrogen environment at the temperature of 125 ℃ for 75 minutes to obtain modified activated carbon fiber;
2) loading the modified activated carbon fiber into an adsorber of an adsorption device; the adsorption device comprises 3 adsorbers, and switching operation of one adsorption state, one drying state and one adsorption saturation state is always kept; the styrene-containing gas firstly enters an adsorber in an adsorption state for adsorption, the styrene is adsorbed on the surface of the activated carbon fiber, the tail gas after adsorption flows out of a bed layer, dry air is supplemented and then the tail gas is sent into the adsorber in a dry state, and the volume ratio of the styrene-containing gas to the supplemented dry air is 4: 1, cooling and drying, and performing secondary adsorption, wherein low-pressure steam enters an adsorber in an adsorption saturated state while adsorption is performed, and the adsorber which finishes adsorption is desorbed;
3) condensing the organic mixed steam generated by desorption in a condenser, and then carrying out liquid-liquid separation in a separator, wherein the upper layer liquid is styrene, and the lower layer liquid is water; 11ppm of polymerization inhibitor is added into the separated styrene, the polymerization inhibitor is a compound polymerization inhibitor of HQ and HPHA according to the mass ratio of 1:10, and the styrene overflows and is recovered.
Example 3
1) Putting activated carbon fibers sold in a T1300 series in a container, taking butanol as a solvent, preparing TMPOP and phosphoric acid or phosphate into an activating solution, uniformly stirring, adding into a glass container, immersing the carbon fibers by about 1 cm in the activating solution at 65 ℃ for 20h, taking out, filtering, drying in the sun, and drying in an oven at 92 ℃ to achieve constant weight; placing the carbon fiber in a muffle furnace, and heating the carbon fiber in a nitrogen environment at the temperature of 160 ℃ for 35 minutes to obtain modified activated carbon fiber;
2) loading the modified activated carbon fiber into an adsorber of an adsorption device; the adsorption device comprises 3 adsorbers, and switching operation of one adsorption state, one drying state and one adsorption saturation state is always kept; the styrene-containing gas firstly enters an adsorber in an adsorption state for adsorption, the styrene is adsorbed on the surface of the activated carbon fiber, the tail gas after adsorption flows out of a bed layer, dry air is supplemented and then the tail gas is sent into the adsorber in a dry state, and the volume ratio of the styrene-containing gas to the supplemented dry air is 2: 1, cooling and drying, and performing secondary adsorption, wherein low-pressure steam enters an adsorber in an adsorption saturated state while adsorption is performed, and the adsorber which finishes adsorption is desorbed;
3) condensing the organic mixed steam generated by desorption in a condenser, and then carrying out liquid-liquid separation in a separator, wherein the upper layer liquid is styrene, and the lower layer liquid is water; adding 12ppm of polymerization inhibitor into the separated styrene, wherein the polymerization inhibitor is a compound polymerization inhibitor of TBC and HPHA according to the mass ratio of 10:1, and overflowing and recovering the styrene.
Example 4
1) Putting activated carbon fibers with a commercial model of T1300 series into a container, using butanol as a solvent, preparing TMPOP and phosphoric acid or phosphate into an activating solution, uniformly stirring, adding into a glass container, wherein the activating solution submerges the carbon fibers by about 1 cm, the soaking temperature is 20 ℃, the soaking time is 24h, taking out, filtering, drying in the sun, and then drying in an oven at 90 ℃ to constant weight; then placing the carbon fiber in a muffle furnace, and heating the carbon fiber in a nitrogen environment at the heating temperature of 105 ℃ for 90 minutes to obtain modified activated carbon fiber;
2) loading the modified activated carbon fiber into an adsorber of an adsorption device; the adsorption device comprises 3 adsorbers, and switching operation of one adsorption state, one drying state and one adsorption saturation state is always kept; the styrene-containing gas firstly enters an adsorber in an adsorption state for adsorption, the styrene is adsorbed on the surface of the activated carbon fiber, the tail gas after adsorption flows out of a bed layer, dry air is supplemented and then the tail gas is sent into the adsorber in a dry state, and the volume ratio of the styrene-containing gas to the supplemented dry air is 6:1, cooling and drying, and performing secondary adsorption, wherein low-pressure steam enters an adsorber in an adsorption saturated state while adsorption is performed, and the adsorber which finishes adsorption is desorbed;
3) condensing the organic mixed steam generated by desorption in a condenser, and then carrying out liquid-liquid separation in a separator, wherein the upper layer liquid is styrene, and the lower layer liquid is water; 10ppm of a polymerization inhibitor, TBC, was added to the separated styrene, and the styrene overflow was recovered.
Example 5
1) Putting activated carbon fibers sold in a T1300 series in a container, taking butanol as a solvent, preparing TMPOP and phosphoric acid or phosphate into an activating solution, uniformly stirring, adding into a glass container, immersing the carbon fibers by about 1 cm in the activating solution at 85 ℃, immersing for 12 hours, taking out, filtering, drying in the sun, and drying in an oven at 95 ℃ to achieve constant weight; placing the carbon fiber in a muffle furnace, and heating the carbon fiber in a nitrogen environment at the temperature of 170 ℃ for 30 minutes to obtain modified activated carbon fiber;
2) loading the modified activated carbon fiber into an adsorber of an adsorption device; the adsorption device comprises 3 adsorbers, and switching operation of one adsorption state, one drying state and one adsorption saturation state is always kept; the styrene-containing gas firstly enters an adsorber in an adsorption state for adsorption, the styrene is adsorbed on the surface of the activated carbon fiber, the tail gas after adsorption flows out of a bed layer, dry air is supplemented and then the tail gas is sent into the adsorber in a dry state, and the volume ratio of the styrene-containing gas to the supplemented dry air is 1:1, cooling and drying, and performing secondary adsorption, wherein low-pressure steam enters an adsorber in an adsorption saturated state while adsorption is performed, and the adsorber which finishes adsorption is desorbed;
3) condensing the organic mixed steam generated by desorption in a condenser, and then carrying out liquid-liquid separation in a separator, wherein the upper layer liquid is styrene, and the lower layer liquid is water; 15ppm of polymerization inhibitor which is HPHA was added to the separated styrene, and the styrene overflow was recovered.
Example 6
1) Putting activated carbon fibers sold in a T1300 series in a container, taking butanol as a solvent, preparing TMPOP and phosphoric acid or phosphate into an activating solution, uniformly stirring, adding into a glass container, immersing the carbon fibers by about 1 cm in the activating solution at normal temperature for 24 hours, taking out, filtering, drying in the sun, and drying in an oven at 92 ℃ for constant weight; then placing the carbon fiber in a muffle furnace, and heating the carbon fiber in a nitrogen environment at the heating temperature of 135 ℃ for 60 minutes to obtain modified activated carbon fiber;
2) loading the modified activated carbon fiber into an adsorber of an adsorption device; the adsorption device comprises 3 adsorbers, and switching operation of one adsorption state, one drying state and one adsorption saturation state is always kept; the styrene-containing gas firstly enters an adsorber in an adsorption state for adsorption, the styrene is adsorbed on the surface of the activated carbon fiber, the tail gas after adsorption flows out of a bed layer, dry air is supplemented and then the tail gas is sent into the adsorber in a dry state, and the volume ratio of the styrene-containing gas to the supplemented dry air is 4: 1, cooling and drying, and performing secondary adsorption, wherein low-pressure steam enters an adsorber in an adsorption saturated state while adsorption is performed, and the adsorber which finishes adsorption is desorbed;
3) condensing the organic mixed steam generated by desorption in a condenser, and then carrying out liquid-liquid separation in a separator, wherein the upper layer liquid is styrene, and the lower layer liquid is water; 12ppm of polymerization inhibitor is added into the separated styrene, the polymerization inhibitor is HQ, and the styrene overflows and is recovered.
Example 7
1) Putting activated carbon fibers sold in a T1300 series in a container, taking butanol as a solvent, preparing TMPOP and phosphoric acid or phosphate into an activating solution, uniformly stirring, adding into a glass container, immersing the carbon fibers by about 1 cm in the activating solution at 60 ℃ for 12h, taking out, filtering, drying in the sun, and drying in an oven at 92 ℃ to achieve constant weight; placing the carbon fiber in a muffle furnace, and heating the carbon fiber in a nitrogen environment at 140 ℃ for 60 minutes to obtain modified activated carbon fiber;
2) loading the modified activated carbon fiber into an adsorber of an adsorption device; the adsorption device comprises 3 adsorbers, and switching operation of one adsorption state, one drying state and one adsorption saturation state is always kept; the styrene-containing gas firstly enters an adsorber in an adsorption state for adsorption, the styrene is adsorbed on the surface of the activated carbon fiber, the tail gas after adsorption flows out of a bed layer, dry air is supplemented and then the tail gas is sent into the adsorber in a dry state, and the volume ratio of the styrene-containing gas to the supplemented dry air is 3:1, cooling and drying, and performing secondary adsorption, wherein low-pressure steam enters an adsorber in an adsorption saturated state while adsorption is performed, and the adsorber which finishes adsorption is desorbed;
3) condensing the organic mixed steam generated by desorption in a condenser, and then carrying out liquid-liquid separation in a separator, wherein the upper layer liquid is styrene, and the lower layer liquid is water; adding 30ppm of polymerization inhibitor into the separated styrene, wherein the polymerization inhibitor is a compound polymerization inhibitor of TBC and DTBHQ according to the mass ratio of 1:1, and overflowing and recovering the styrene.
Example 8
1) Putting activated carbon fibers sold in a T1300 series in a container, taking butanol as a solvent, preparing TMPOP and phosphoric acid or phosphate into an activating solution, uniformly stirring, adding into a glass container, immersing the carbon fibers by about 1 cm in the activating solution at 60 ℃ for 12h, taking out, filtering, drying in the sun, and drying in an oven at 92 ℃ to achieve constant weight; placing the carbon fiber in a muffle furnace, and heating the carbon fiber in a nitrogen environment at 140 ℃ for 60 minutes to obtain modified activated carbon fiber;
2) loading the modified activated carbon fiber into an adsorber of an adsorption device; the adsorption device comprises 3 adsorbers, and switching operation of one adsorption state, one drying state and one adsorption saturation state is always kept; the styrene-containing gas firstly enters an adsorber in an adsorption state for adsorption, the styrene is adsorbed on the surface of the activated carbon fiber, the tail gas after adsorption flows out of a bed layer, dry air is supplemented and then the tail gas is sent into the adsorber in a dry state, and the volume ratio of the styrene-containing gas to the supplemented dry air is 3:1, cooling and drying, and performing secondary adsorption, wherein low-pressure steam enters an adsorber in an adsorption saturated state while adsorption is performed, and the adsorber which finishes adsorption is desorbed;
3) condensing the organic mixed steam generated by desorption in a condenser, and then carrying out liquid-liquid separation in a separator, wherein the upper layer liquid is styrene, and the lower layer liquid is water; 30ppm of polymerization inhibitor is added into the separated styrene, the polymerization inhibitor is DTBHQ, and the styrene overflows and is recovered.
Example 9
1) Putting activated carbon fibers sold in a T1300 series in a container, taking butanol as a solvent, preparing TMPOP and phosphoric acid or phosphate into an activating solution, uniformly stirring, adding into a glass container, immersing the carbon fibers by about 1 cm in the activating solution at normal temperature for 12h, taking out, filtering, drying in the sun, and drying in an oven at 92 ℃ for constant weight; placing the carbon fiber in a muffle furnace, and heating the carbon fiber in a nitrogen environment at 140 ℃ for 60 minutes to obtain modified activated carbon fiber;
2) loading the modified activated carbon fiber into an adsorber of an adsorption device; the adsorption device comprises 3 adsorbers, and switching operation of one adsorption state, one drying state and one adsorption saturation state is always kept; the styrene-containing gas firstly enters an adsorber in an adsorption state for adsorption, the styrene is adsorbed on the surface of the activated carbon fiber, the tail gas after adsorption flows out of a bed layer, dry air is supplemented and then the tail gas is sent into the adsorber in a dry state, and the volume ratio of the styrene-containing gas to the supplemented dry air is 3:1, cooling and drying, and performing secondary adsorption, wherein low-pressure steam enters an adsorber in an adsorption saturated state while adsorption is performed, and the adsorber which finishes adsorption is desorbed;
3) condensing the organic mixed steam generated by desorption in a condenser, and then carrying out liquid-liquid separation in a separator, wherein the upper layer liquid is styrene, and the lower layer liquid is water; 30ppm of polymerization inhibitor is added into the separated styrene, the polymerization inhibitor is DTBHQ, and the styrene overflows and is recovered.
The processing steps of comparative examples 1 and 2 were the same as in example 1, and the effects of using different activators on activated carbon fibers are shown in Table 1.
TABLE 1 Effect of Using different activators on activated carbon fibers
Note: comparative example 1 is the result of the specific surface area test of a commercially available T1300 activated carbon fiber before modification.
As can be seen from the experimental data in Table 1, the carbon fiber has a significantly increased specific surface area after modification as compared with comparative example 1, which is 1050 m before modification2The ratio of/g is increased to 1450m2The specific surface area is improved by more than 38 percent at least by more than g, and is gradually improved along with the improvement of the concentration of the activating agent, and the concentration is preferably 6-10 percent, and most preferably 6 percent. Under the condition that the concentration of the activator is 5%, the TMPOP + monopotassium phosphate compound composition has the best effect as the activator.
The polymerization inhibiting performance of the modified activated carbon fibers was performed in a 500 ml four-necked flask. Styrene and the activated carbon fibers of example 1 and comparative example 1 were weighed in a certain amount and charged into two four-necked flasks, 25g of the activated carbon fiber of example 1 of the present invention was charged into one of the four-necked flasks, 25g of the same commercially available T1300 activated carbon fiber was charged into the other four-necked flask, 25g of the same was charged into the other four-necked flask, a condenser was added above each four-necked flask, air in the system was replaced with nitrogen for 5 to 10 minutes to reduce the oxygen content in the flask, the system was sealed, the four-necked flask was heated in a constant temperature heater and kept at a constant temperature of 125 ℃ for 24 hours during which styrene polymer was deposited in the carbon fibers. And then cooling, taking out the carbon fiber, drying and weighing, wherein the experimental result is shown in table 2.
TABLE 2 polymerization inhibiting Properties of different carbon fibers
The data in table 2 show that no significant weight gain was observed with the modified carbon fibers of the invention; commercial T1300 carbon fibers from another flask, taken out, showed significant polymer deposition after heating, increasing the weight by 1.52%. Therefore, the modified activated carbon fiber has an obvious polymerization inhibition function.
Adsorption of styrene waste gas: the adsorption device comprises 3 adsorbers with the same size, one adsorber is always in an adsorption state, the other adsorber is always in a drying state, the other adsorber is always in a desorption state, and the operation is switched. The adsorber is made of carbon steel and has the size phi 70 x 5 x 700, and activated carbon fibers are filled in the adsorber in a spiral state. The styrene-containing gas first enters the adsorber A in an adsorption state from the lower part to be adsorbed, and styrene is adsorbed on the surfaces of the activated carbon fibers. The adsorber is provided with a jacket, cooling water is filled in the jacket, adsorption heat generated in the adsorption process can be removed in time to improve the adsorption effect, potential safety hazards formed after heat release, accumulation and temperature rise are avoided, and the adsorption temperature is controlled below 35 ℃. And the tail gas after adsorption flows out from the top of the adsorber, is mixed with dry air and then is sent into the adsorber B from the bottom to be subjected to cooling drying and secondary adsorption, and the tail gas after adsorption is discharged from the top. And when the adsorption is carried out, low-pressure steam enters the adsorber C in an adsorption saturated state from the top, and the adsorber C which finishes the adsorption is desorbed. The desorption liquid enters a separator after being condensed, the upper oil phase is the recycled styrene, and 15ppm of TBC is added into the oil phase and can be sold as a product.
The modified activated carbon fibers obtained in the manner described in the examples were loaded into an adsorber. Wherein the fixed conditions are as follows: the adsorption temperature is 25-30 ℃, the gas velocity is 420L/h, and the loading amount of the activated carbon fiber in each adsorber is 120 g.
It is noted that comparative example 1 added a commercial T1300 carbon fiber, which was not modified using the process of the present invention. The activated carbon fibers used in comparative examples 3 and 4 were the same as those used in example 4, and modified activated carbon fibers were used; comparative example 3, in which no interlayer cooling was used; comparative example 4 employs a first stage adsorption without entering adsorber B for drying and adsorption, and the experimental results are detailed in table 3.
Table 3 adsorption experiment results
As can be seen from the data in Table 3, with the increase of the styrene concentration at the inlet of the adsorber, the styrene concentration at the outlet of the two-stage adsorption can be lower than 50mg/m3The removal rate is more than 99.5 percent, the removal rate of unmodified activated carbon fibers is only 81.9 percent, and the removal rate is less than 98 percent without timely cooling and primary adsorption.
The carbon fibers were unloaded and dried after 5 cycles of adsorption and desorption in example 1 and comparative example 1, and the results are shown in table 4.
TABLE 4 Performance of activated carbon fiber
Note: example 1 specific surface area 1885m before adsorber filling2Comparative example 1 specific surface area 1050 m/g2/g。
As can be seen from the data in Table 4, the carbon fiber of comparative example 1 has a significantly reduced specific surface area after 5 times of adsorption and desorption, the carbon fiber has a significant slag drop phenomenon, the flexibility changes greatly, the carbon fiber has a weight increase of 0.9 g, and the carbon fiber has a weight increase of 0.75%, indicating that a polymer is generated. The specific surface area of the carbon fiber in the embodiment 1 is basically unchanged, and the weight is not increased, which shows that the carbon fiber has a polymerization inhibiting function, and obviously and effectively avoids the polymerization phenomenon of styrene.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (6)
1. A styrene waste gas treatment method is characterized in that the treatment steps comprise:
1) dipping carbon fiber in butanol solution containing tris (2, 2,6, 6-tetramethyl-4-hydroxy-piperidinyloxy) phosphine and phosphoric acid, or tris (2, 2,6, 6-tetramethyl-4-hydroxy-piperidinyloxy) phosphine and phosphate, wherein the mass ratio of tris (2, 2,6, 6-tetramethyl-4-hydroxy-piperidinyloxy) phosphine and phosphoric acid, or tris (2, 2,6, 6-tetramethyl-4-hydroxy-piperidinyloxy) phosphine and phosphate is 0.6-3: 1, the total mass concentration of tris (2, 2,6, 6-tetramethyl-4-hydroxy-piperidinyloxy) phosphine and phosphoric acid or phosphate is 1-10%, the dipping time is 10-36 h, filtering the solution, heating and activating in inert gas at the temperature of 105-170 ℃, and cooling to obtain modified activated carbon fibers;
2) loading the modified activated carbon fiber into an adsorber of an adsorption device; the adsorption device comprises 3 adsorbers, and switching operation of one adsorption state, one drying state and one adsorption saturation state is always kept; the method comprises the following steps that styrene-containing gas firstly enters an adsorber in an adsorption state for adsorption, styrene is adsorbed on the surface of activated carbon fibers, tail gas after adsorption flows out of a bed layer, dry air is supplemented and then the tail gas is sent into the adsorber in a dry state for cooling and drying and secondary adsorption, low-pressure steam enters the adsorber in an adsorption saturated state while adsorption is carried out, and the adsorber after adsorption is desorbed;
3) condensing the organic mixed steam generated by desorption in a condenser, and then carrying out liquid-liquid separation in a separator, wherein the upper layer liquid is styrene, and the lower layer liquid is water; 10-30 ppm of polymerization inhibitor is added into the separated styrene, and the styrene overflows and is recovered.
2. The styrene off-gas treatment method according to claim 1, wherein: the total concentration of the tris (2, 2,6, 6-tetramethyl-4-hydroxy-piperidinyloxy) phosphine and phosphoric acid or the tris (2, 2,6, 6-tetramethyl-4-hydroxy-piperidinyloxy) phosphine and phosphate in butanol in the step 1) is 2-6%.
3. The styrene off-gas treatment method according to claim 1, wherein: the phosphate in the step 1) is sodium dihydrogen phosphate, potassium dihydrogen phosphate or ammonium dihydrogen phosphate.
4. The styrene off-gas treatment method according to claim 1, wherein: the dipping temperature in the step 1) is 20-85 ℃, and the dipping time is 12-24 h.
5. The styrene off-gas treatment method according to claim 1, wherein: the volume ratio of the styrene-containing gas to the supplementary dry air in the step 2) is 1-6: 1.
6. the styrene off-gas treatment method according to claim 1, wherein: the polymerization inhibitor in the step 3) is a storage type polymerization inhibitor TBC, HQ, hydroxylamine compound or a compound of two of the TBC, the HQ and the hydroxylamine compound.
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