CN110756161A - Process method for treating octanol waste gas pollution - Google Patents
Process method for treating octanol waste gas pollution Download PDFInfo
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- CN110756161A CN110756161A CN201810844351.9A CN201810844351A CN110756161A CN 110756161 A CN110756161 A CN 110756161A CN 201810844351 A CN201810844351 A CN 201810844351A CN 110756161 A CN110756161 A CN 110756161A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
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Abstract
A process method for treating octanol waste gas pollution belongs to the technical field of treatment methods of organic pollutants in waste gas. The method is characterized in that: the treatment process comprises the following steps: soaking carbon fiber in the activating solution by taking a compound of aryl phosphine or a derivative thereof and phosphoric acid or phosphate as an activating agent, heating and activating in inert gas, and cooling to obtain modified activated carbon fiber; loading activated carbon fiber into an adsorber of an adsorption device; the gas containing octanol firstly enters an absorber for adsorption, and the absorber which finishes adsorption is desorbed; and 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 organic octanol, the lower layer liquid is water, and octanol is recovered in an overflowing manner. The method has high desorption efficiency and long service life of the activated carbon fiber, and fundamentally solves the problem of low octanol absorption and desorption efficiency.
Description
Technical Field
A process method for treating octanol waste gas pollution belongs to the technical field of treatment methods of organic pollutants in waste gas.
Background
Octanol is a colorless, transparent, oily liquid with an irritating odor, a boiling point (normal atmospheric pressure) of 185 ℃ and a vapor pressure (20 ℃) of 66.66 Pa. Octanol is an important chemical basic raw material and solvent, and is mainly used for preparing phthalate and aliphatic dibasic acid ester plasticizers such as dioctyl phthalate, dioctyl azelate, dioctyl sebacate and diisooctyl phosphate; solvents for adhesives, dehydrating agents for detergents; defoaming agents for photographic paper making, painting, printing and dyeing and other processes; dispersant of ceramic industry oil slurry; beneficiation agents, cleaning agents, petroleum additives, and the like.
In the production, storage and loading processes of octanol, 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 waste gas leakage exists in the actual operation, the octanol content cannot reach the discharge standard specified by the state in the direct exhaust of loading tail gas and a production device, the recovery treatment is needed, and the problem of environment pollution caused by waste gas is fundamentally solved.
The common treatment method of the organic waste gas comprises absorption, adsorption, condensation, combustion and membrane separation, and the valuable organic substances in the waste gas are recovered by adopting the condensation, adsorption, membrane separation or the combination method thereof. With the strictness of national environmental regulations, the activated carbon adsorption method has become a research hotspot for scholars at home and abroad in recent years.
Chinese patent CN200310101839.6 discloses a device and method for adsorbing, recovering and treating organic waste gas by activated carbon fiber, which is characterized in that: the recovery device comprises a rectification recovery system for recovering the organic solvent in the organic solvent, wherein the rectification recovery system comprises a rectification tower positioned between a desorption gas outlet and a condenser and a solvent receiving groove positioned after 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 the organic pollutants with high boiling points 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, and the pollution of powdered activated carbon to the environment is greatly reduced, but the conventional organic pollutants with lower boiling points are treated, and the boiling points are about 100 ℃.
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 specific surface area of the product is 800-3200 m2(ii) a pore size distribution of 0.6 to 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 process method for treating octanol waste gas pollution with high adsorption efficiency and high temperature resistance.
The technical scheme adopted by the invention for solving the technical problems is as follows: the technical method for treating octanol waste gas pollution is characterized in that the treatment process comprises the following steps:
1) taking a compound of aryl phosphine or a derivative thereof and phosphoric acid or phosphate as an activating agent, and taking butanol as a solvent to prepare an activating solution with a total mass concentration of 1-10%, wherein the mass ratio of the aryl phosphine or the derivative thereof to the phosphoric acid or phosphate is (0.18-6): 1, soaking carbon fibers in the activating solution for 10-36 hours, then filtering the activating solution, heating and activating in inert gas at the temperature of 120-200 ℃, 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 three adsorbers which are always kept in a switching operation of one adsorption state, one drying state and one adsorption saturation state; the method comprises the following steps of (1) enabling octanol-containing gas to enter an adsorber in an adsorption state for adsorption, enabling octanol to be adsorbed on the surface of activated carbon fibers, enabling tail gas after adsorption to flow out of a bed layer, supplementing dry air, sending the gas into the adsorber in a dry state, performing cooling drying and secondary adsorption, enabling low-pressure steam to enter the adsorber in an adsorption saturated state while adsorption is performed, and performing desorption on the adsorber after adsorption;
3) and 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 organic octanol, the lower layer liquid is water, and octanol is recovered in an overflowing manner.
According to the invention, aryl phosphine or derivatives thereof and phosphoric acid or phosphate are compounded to modify the carbon fiber, the fiber is activated, the carbon skeleton is rearranged, a large number of pore structures are created, the specific surface is enlarged, the activated carbon fiber is endowed with stronger adsorption force and high temperature resistance, the active carbon fiber has high desorption efficiency and long service life in the desorption process of octanol at the temperature of more than 185 ℃, the problem that the emission standard is difficult to reach after the octanol is adsorbed in waste gas due to low adsorption and desorption rate and difficult regeneration of the active carbon fiber in the existing octanol adsorption technology is solved, and the use efficiency of the active carbon fiber is improved.
Preferably, the aryl phosphine described in step 1) is triphenylphosphine, triphenylphosphine oxide, diphenylphosphine, alkyldiphenylphosphine or/and tri-o-tolylphosphine. The preferred aryl phosphine can form a finer pore structure by modifying the carbon fiber, so that the specific surface of the carbon fiber is larger, and the activated carbon fiber has stronger adsorption force and better high-temperature resistance.
More preferably, the aryl phosphine described in step 1) is triphenylphosphine. The more preferable aryl phosphine can form a finer pore structure by modifying the carbon fiber, 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.
Preferably, the arylphosphine derivative in the step 1) is carbethoxyethylidene triphenylphosphine, carbomethoxyethylidene triphenylphosphine, carbethoxymethylene triphenylphosphine or/and carbomethoxymethylene triphenylphosphine. The preferred aryl phosphine derivative can form a finer pore structure by modifying the carbon fiber, so that the specific surface of the carbon fiber is larger, and the activated carbon fiber has stronger adsorption force and better high-temperature resistance.
Preferably, the total mass concentration of the aryl phosphine or the derivative thereof and the phosphoric acid or the phosphate in the butanol in the step 1) is 1-8%. The carbon fiber is modified by the optimal solution concentration 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 high-temperature resistance.
Preferably, the total mass concentration of the aryl phosphine or the derivative thereof 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.
Preferably, the phosphate in step 1) is a hydrogen phosphate, including monohydrogen phosphate, dihydrogen phosphate, preferably sodium dihydrogen phosphate, potassium dihydrogen phosphate or/and ammonium dihydrogen phosphate. The carbon fiber is modified by the optimized 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 high-temperature resistance.
Preferably, the mass ratio of the aryl phosphine or the derivative thereof to the phosphoric acid or the phosphate in the step 1) is 0.25-4: 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 high temperature resistance.
Preferably, the mass ratio of the aryl phosphine or the derivative thereof to the phosphoric acid or the phosphate in the step 1) is 0.5-3: 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 high temperature resistance of the activated carbon fiber can achieve the best performance.
Preferably, the temperature in the dipping process in the step 1) is 20-75 ℃, 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 20-75 ℃, 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 to enhance the adsorption force. 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 aryl phosphine or derivatives thereof 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 active functional groups are formed on the surface of the raw material carbon fibers, and the active carbon fibers with further improved performance are obtained.
In step 2), filling activated carbon fibers into an adsorber, switching the adsorption of octanol waste gas in 3 adsorbers, allowing the waste gas to enter the adsorber in an adsorption state from the bottom, allowing octanol gas to be adsorbed by the activated carbon fibers and 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 octanol concentration at the 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 from the top of the adsorber 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 octanol waste gas, octanol which is not completely adsorbed by the adsorber A can be subjected to secondary adsorption, and the content of octanol in tail gas after adsorption can be ensured to be lower than the national emission requirement. Wherein, the mixing proportion of the octanol-containing waste gas and the dry air is waste gas: air (V/V) = 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 method adopts low-pressure steam to desorb the octanol, and the desorption effect is good.
In the step 3), after the octanol is desorbed by the steam, the mixed steam containing the octanol enters a condenser for condensation, and the cooling medium is cooling water. When the boiling point of octanol is lower than the cooling water temperature, it can be condensed. The temperature of the oil-water mixture can be reduced to below 35 ℃ by cooling through a condenser. And (3) the oil-water mixture obtained by condensation enters an oil-water separator, and octanol is fully separated from water. And the octanol overflows into the metering tank after the liquid level of the separator reaches a certain height, and is recovered as a product.
Compared with the prior art, the invention has the beneficial effects that: the process method for treating octanol waste gas pollution is different from the adsorption and process effects of activated carbon fibers in the prior art, the specific surface of the activated carbon fibers is increased by adopting an aryl phosphine or derivatives thereof and an activating agent formula of phosphoric acid or phosphate in the activation process of the carbon fibers through impregnation and fiber activation, and the activated carbon fibers are endowed with stronger adsorption force and high temperature resistance; two-stage adsorption is adopted, wherein the first stage adopts jacket internal circulation cooling for timely taking away adsorption heat, thus effectively improving the recovery rate of octanol, eliminating the phenomenon of adsorption heat accumulation and prolonging the service life of the activated carbon fiber; the second adsorption plays a role in cooling; meanwhile, the octanol content in the tail gas after adsorption can be ensured to be 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 octanol waste gas with high boiling point and high concentration.
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 working examples and comparative examples were conducted in the following manner.
Example 1
1) The method comprises the steps of adopting commercially available T1300 series activated carbon fibers, using butanol as a solvent, preparing aryl phosphine or derivatives thereof and phosphoric acid or phosphate into activating solution with the concentration of about 1 cm according to a proportion, uniformly stirring, immersing the carbon fibers in the activating solution, taking out, filtering, drying in the sun, and drying in an oven at 95 ℃ for constant weight, wherein the carbon fibers are immersed in the activating solution for about 1 cm. Placing the carbon fiber in a muffle furnace, and heating the carbon fiber in a nitrogen environment at the temperature of 160 ℃ 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 method comprises the following steps of (1) enabling octanol-containing gas to enter an adsorber in an adsorption state for adsorption, enabling octanol to be adsorbed on the surface of activated carbon fibers, enabling tail gas after adsorption to flow out of a bed layer, supplementing dry air, sending the gas into the adsorber in a dry state, performing cooling drying and secondary adsorption, enabling low-pressure steam to enter the adsorber in an adsorption saturated state while adsorption is performed, and performing desorption on the adsorber after adsorption;
3) and 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 organic octanol, the lower layer liquid is water, and the octanol overflows into a metering tank for recovery.
Example 2
1) The method comprises the steps of adopting commercially available T1300 series activated carbon fibers, using butanol as a solvent, preparing aryl phosphine or derivatives thereof and phosphoric acid or phosphate into activating solution with the concentration of about 1 cm according to a proportion, uniformly stirring, immersing the carbon fibers in the activating solution, taking out, filtering, drying in the sun, and drying in an oven at 92 ℃ for constant weight, wherein the carbon fibers are immersed in the activating solution for about 1 cm. Placing the carbon fiber in a muffle furnace, and heating the carbon fiber in a nitrogen environment at 140 ℃ 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 method comprises the following steps of (1) enabling octanol-containing gas to enter an adsorber in an adsorption state for adsorption, enabling octanol to be adsorbed on the surface of activated carbon fibers, enabling tail gas after adsorption to flow out of a bed layer, supplementing dry air, sending the gas into the adsorber in a dry state, performing cooling drying and secondary adsorption, enabling low-pressure steam to enter the adsorber in an adsorption saturated state while adsorption is performed, and performing desorption on the adsorber after adsorption;
3) and 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 organic octanol, the lower layer liquid is water, and the octanol overflows into a metering tank for recovery.
Example 3
1) The method comprises the steps of adopting commercially available T1300 series activated carbon fibers, using butanol as a solvent, preparing aryl phosphine or derivatives thereof and phosphoric acid or phosphate into activating solution with the concentration of about 1 cm according to a proportion, uniformly stirring, immersing the carbon fibers in the activating solution, taking out, filtering, drying in the sun, and drying in an oven at 98 ℃ for constant weight, wherein the carbon fibers are immersed in the activating solution for about 1 cm. Placing the carbon fiber in a muffle furnace, and heating the carbon fiber in a nitrogen environment at the temperature of 180 ℃ 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 method comprises the following steps of (1) enabling octanol-containing gas to enter an adsorber in an adsorption state for adsorption, enabling octanol to be adsorbed on the surface of activated carbon fibers, enabling tail gas after adsorption to flow out of a bed layer, supplementing dry air, sending the gas into the adsorber in a dry state, performing cooling drying and secondary adsorption, enabling low-pressure steam to enter the adsorber in an adsorption saturated state while adsorption is performed, and performing desorption on the adsorber after adsorption;
3) and 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 organic octanol, the lower layer liquid is water, and the octanol overflows into a metering tank for recovery.
Example 4
1) The method comprises the steps of adopting activated carbon fibers with a commercial model of T1300 series, taking butanol as a solvent, respectively preparing aryl phosphine or derivatives thereof and phosphoric acid or phosphate into activating liquid with a concentration of about 1 cm according to a proportion, uniformly stirring, immersing the carbon fibers in the activating liquid, taking out, filtering, drying in the sun, and drying in an oven at 90 ℃ for a constant weight, wherein the temperature in the immersing process is 20 ℃ and the immersing time is 12 h. Placing the carbon fiber in a muffle furnace, and heating the carbon fiber in a nitrogen environment at the heating temperature of 120 ℃ 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 method comprises the following steps of (1) enabling octanol-containing gas to enter an adsorber in an adsorption state for adsorption, enabling octanol to be adsorbed on the surface of activated carbon fibers, enabling tail gas after adsorption to flow out of a bed layer, supplementing dry air, sending the gas into the adsorber in a dry state, performing cooling drying and secondary adsorption, enabling low-pressure steam to enter the adsorber in an adsorption saturated state while adsorption is performed, and performing desorption on the adsorber after adsorption;
3) and 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 organic octanol, the lower layer liquid is water, and the octanol overflows into a metering tank for recovery.
Example 5
1) The method comprises the steps of preparing activated carbon fibers of T1300 series on the market, taking butanol as a solvent, preparing aryl phosphine or derivatives thereof and phosphoric acid or phosphate into activating liquid according to a certain proportion, uniformly stirring, immersing the carbon fibers in the activating liquid for about 1 cm by the activating liquid, immersing the carbon fibers at 75 ℃ for 12h, taking out, filtering, drying in the sun, and drying in an oven at 100 ℃ for constant weight. Placing the carbon fiber in a muffle furnace, and heating the carbon fiber in a nitrogen environment at the heating temperature of 200 ℃ 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 method comprises the following steps of (1) enabling octanol-containing gas to enter an adsorber in an adsorption state for adsorption, enabling octanol to be adsorbed on the surface of activated carbon fibers, enabling tail gas after adsorption to flow out of a bed layer, supplementing dry air, sending the gas into the adsorber in a dry state, performing cooling drying and secondary adsorption, enabling low-pressure steam to enter the adsorber in an adsorption saturated state while adsorption is performed, and performing desorption on the adsorber after adsorption;
3) and 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 organic octanol, the lower layer liquid is water, and the octanol overflows into a metering tank for recovery.
Example 6
1) The method comprises the steps of adopting activated carbon fibers with a commercial model of T1300 series, taking butanol as a solvent, preparing aryl phosphine or derivatives thereof and phosphoric acid or phosphate into activating liquid according to a proportion, uniformly stirring, soaking the carbon fibers in the activating liquid, wherein the activating liquid submerges the carbon fibers by about 1 cm, taking out, filtering, drying in the sun, and drying in an oven at 90 ℃ for constant weight, wherein the temperature in the soaking process is 75 ℃, and the soaking time is 10 hours. Placing the carbon fiber in a muffle furnace, and heating the carbon fiber in a nitrogen environment at the heating temperature of 120 ℃ 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 method comprises the following steps of (1) enabling octanol-containing gas to enter an adsorber in an adsorption state for adsorption, enabling octanol to be adsorbed on the surface of activated carbon fibers, enabling tail gas after adsorption to flow out of a bed layer, supplementing dry air, sending the gas into the adsorber in a dry state, performing cooling drying and secondary adsorption, enabling low-pressure steam to enter the adsorber in an adsorption saturated state while adsorption is performed, and performing desorption on the adsorber after adsorption;
3) and 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 organic octanol, the lower layer liquid is water, and the octanol overflows into a metering tank for recovery.
Example 7
1) The method comprises the steps of adopting commercially available T1300 series activated carbon fibers, using butanol as a solvent, preparing aryl phosphine or derivatives thereof and phosphoric acid or phosphate into activating solution with the concentration of about 1 cm according to a proportion, uniformly stirring, immersing the carbon fibers in the activating solution, taking out, filtering, drying in the sun, and drying in an oven at 100 ℃ for a constant weight, wherein the carbon fibers are immersed in the activating solution for about 1 cm. Placing the carbon fiber in a muffle furnace, and heating the carbon fiber in a nitrogen environment at the heating temperature of 120 ℃ 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 method comprises the following steps of (1) enabling octanol-containing gas to enter an adsorber in an adsorption state for adsorption, enabling octanol to be adsorbed on the surface of activated carbon fibers, enabling tail gas after adsorption to flow out of a bed layer, supplementing dry air, sending the gas into the adsorber in a dry state, performing cooling drying and secondary adsorption, enabling low-pressure steam to enter the adsorber in an adsorption saturated state while adsorption is performed, and performing desorption on the adsorber after adsorption;
3) and 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 organic octanol, the lower layer liquid is water, and the octanol overflows into a metering tank for recovery.
Example 8
1) The method comprises the steps of adopting activated carbon fibers with a commercial model of T1300 series, taking butanol as a solvent, preparing aryl phosphine or derivatives thereof and phosphoric acid or phosphate into activating liquid with a concentration of about 1 cm according to a proportion, uniformly stirring, immersing the carbon fibers in the activating liquid, taking out, filtering, drying in the sun, and drying in an oven at 95 ℃ for a constant weight, wherein the temperature in the immersing process is normal temperature, and the immersing time is 20 hours. Placing the carbon fiber in a muffle furnace, and heating the carbon fiber in a nitrogen environment at the temperature of 160 ℃ for 80 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 method comprises the following steps of (1) enabling octanol-containing gas to enter an adsorber in an adsorption state for adsorption, enabling octanol to be adsorbed on the surface of activated carbon fibers, enabling tail gas after adsorption to flow out of a bed layer, supplementing dry air, sending the gas into the adsorber in a dry state, performing cooling drying and secondary adsorption, enabling low-pressure steam to enter the adsorber in an adsorption saturated state while adsorption is performed, and performing desorption on the adsorber after adsorption;
3) and 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 organic octanol, the lower layer liquid is water, and the octanol overflows into a metering tank for recovery.
Example 9
1) The method comprises the steps of adopting commercially available T1300 series activated carbon fibers, using butanol as a solvent, preparing aryl phosphine or derivatives thereof and phosphoric acid or phosphate into activating solution with the concentration of about 1 cm according to a proportion, uniformly stirring, immersing the carbon fibers in the activating solution, taking out, filtering, drying in the sun, and drying in an oven at 95 ℃ for constant weight, wherein the carbon fibers are immersed in the activating solution for about 1 cm. Placing the carbon fiber in a muffle furnace, and heating the carbon fiber in a nitrogen environment at the temperature of 160 ℃ 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 method comprises the following steps of (1) enabling octanol-containing gas to enter an adsorber in an adsorption state for adsorption, enabling octanol to be adsorbed on the surface of activated carbon fibers, enabling tail gas after adsorption to flow out of a bed layer, supplementing dry air, sending the gas into the adsorber in a dry state, performing cooling drying and secondary adsorption, enabling low-pressure steam to enter the adsorber in an adsorption saturated state while adsorption is performed, and performing desorption on the adsorber after adsorption;
3) and 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 organic octanol, the lower layer liquid is water, and the octanol overflows into a metering tank for recovery.
The processing steps of comparative examples 1 and 2 were the same as in example 1.
TABLE 1 Effect of Using different activators on activated carbon fibers
Note: comparative 10 is the specific surface area test result of the commercial 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/g is increased to 1500m2The specific surface area is improved by more than 42 percent, wherein the triphenylphosphine and ammonium dihydrogen phosphate compound composition has the best effect as an activator.
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 gas containing octanol firstly enters the adsorber A in the adsorption state from the lower part for adsorption, and the octanol is adsorbed on the surface of the activated carbon fiber. 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, and the upper oil phase is recovered octanol which can be sold as a product.
The modified activated carbon fibers obtained 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 360L/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 first-stage adsorption without entering adsorber B for drying and adsorption, and the experimental results are detailed in table 2.
Table 2 adsorption experiment results
As can be seen from the data in Table 2, the concentration of octanol at the outlet after two-stage adsorption can be lower than 50 mg/m along with the increase of the concentration of octanol at the inlet of the adsorber3The removal rate is more than 99.5 percent, the removal rate of unmodified activated carbon fibers is only 80.8 percent, and the removal rate is less than 98 percent without timely cooling and primary adsorption.
The carbon fibers of example 4 and comparative example 1 were unloaded after 5 adsorption and desorption cycles, dried and analyzed for properties, and the results are shown in table 3.
TABLE 3 Performance of activated carbon fiber
Note: the activated carbon fibers of example 4 and comparative example 1 were 3.5mm thick prior to the first loading into the adsorber.
The data in table 3 show that the carbon fiber of comparative example 1 has a reduced specific surface area after 5 times of adsorption and desorption, and the carbon fiber has obvious slag falling phenomenon and large flexibility change.
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 (10)
1. A process method for treating octanol waste gas pollution is characterized in that: the treatment process comprises the following steps:
1) taking a compound of aryl phosphine or a derivative thereof and phosphoric acid or phosphate as an activating agent, and taking butanol as a solvent to prepare an activating solution with a total mass concentration of 1-10%, wherein the mass ratio of the aryl phosphine or the derivative thereof to the phosphoric acid or phosphate is (0.18-6): 1, soaking carbon fibers in the activating solution for 10-36 hours, then filtering the activating solution, heating and activating in inert gas at the temperature of 120-200 ℃, 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 three adsorbers which are always kept in a switching operation of one adsorption state, one drying state and one adsorption saturation state; the method comprises the following steps of (1) enabling octanol-containing gas to enter an adsorber in an adsorption state for adsorption, enabling octanol to be adsorbed on the surface of activated carbon fibers, enabling tail gas after adsorption to flow out of a bed layer, supplementing dry air, sending the gas into the adsorber in a dry state, performing cooling drying and secondary adsorption, enabling low-pressure steam to enter the adsorber in an adsorption saturated state while adsorption is performed, and performing desorption on the adsorber after adsorption;
3) and 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 organic octanol, the lower layer liquid is water, and octanol is recovered in an overflowing manner.
2. The process of claim 1 for treating octanol waste gas pollution, wherein: the aryl phosphine in the step 1) is triphenylphosphine, triphenylphosphine oxide, diphenylphosphine, alkyl diphenylphosphine or/and tri-o-tolylphosphine.
3. The process of claim 1 for treating octanol waste gas pollution, wherein: the aryl phosphine in the step 1) is triphenylphosphine.
4. The process of claim 1 for treating octanol waste gas pollution, wherein: the aryl phosphine derivative in the step 1) is carbethoxyethylidene triphenylphosphine, carbomethoxyethylidene triphenylphosphine, carbethoxymethylene triphenylphosphine or/and carbomethoxymethylene triphenylphosphine.
5. The process of claim 1 for treating octanol waste gas pollution, wherein: the total mass concentration of the aryl phosphine or the derivative thereof and the phosphoric acid or the phosphate in the butanol in the step 1) is 1-8%.
6. The process of claim 1 for treating octanol waste gas pollution, wherein: the total mass concentration of the aryl phosphine or the derivative thereof and the phosphoric acid or the phosphate in the butanol in the step 1) is 2-6%.
7. The process of claim 1 for treating octanol waste gas pollution, wherein: the phosphate in the step 1) is sodium dihydrogen phosphate, potassium dihydrogen phosphate or/and ammonium dihydrogen phosphate.
8. The process of claim 1 for treating octanol waste gas pollution, wherein: the mass ratio of the aryl phosphine or the derivative thereof to the phosphoric acid or the phosphate in the step 1) is 0.25-4: 1.
9. The process of claim 1 for treating octanol waste gas pollution, wherein: the mass ratio of the aryl phosphine or the derivative thereof to the phosphoric acid or the phosphate in the step 1) is 0.5-3: 1.
10. The process of claim 1 for treating octanol waste gas pollution, wherein: the temperature in the dipping process in the step 1) is 20-75 ℃, and the dipping time is 12-24 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115672271A (en) * | 2022-10-25 | 2023-02-03 | 山东格瑞德环保科技有限公司 | Modified activated carbon for oil gas recovery and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4520623A (en) * | 1982-07-17 | 1985-06-04 | Toho Beslon Co., Ltd. | Activated carbon fiber spun yarn |
| CN1295142A (en) * | 2000-10-28 | 2001-05-16 | 中山大学 | Phosphoric acid activation process of producing active carbon fiber |
| CN1765489A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | Supported type active carbon and its preparation method |
| CN101288820A (en) * | 2008-06-13 | 2008-10-22 | 北京云辰天环保科技有限公司 | Active carbon fiber organic gas recovery method and system using nitrogen as desorption medium |
| US20090048467A1 (en) * | 2007-08-13 | 2009-02-19 | Headwaters Technology Innovation, Llc | Methods for making immobilized aryl-containing ligands |
| CN203447939U (en) * | 2013-01-31 | 2014-02-26 | 东洋纺株式会社 | Gas processing device |
| CN104906917A (en) * | 2014-03-12 | 2015-09-16 | 北京日新达能技术有限公司 | Method for multistage adsorption and recovery of organic gases through active carbon fiber |
| US20160361704A1 (en) * | 2012-04-25 | 2016-12-15 | Lg Chem, Ltd. | Super absorbent polymer and a preparation method thereof |
| CN106824267A (en) * | 2017-01-25 | 2017-06-13 | 江西省汉氏贵金属有限公司 | A kind of Suzuki coupling reactions palladium-carbon catalyst and preparation method thereof |
| CN107651651A (en) * | 2017-09-29 | 2018-02-02 | 浙江工业大学 | A kind of porosu solid supported ion liquid of absorption HCl gases |
-
2018
- 2018-07-27 CN CN201810844351.9A patent/CN110756161B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4520623A (en) * | 1982-07-17 | 1985-06-04 | Toho Beslon Co., Ltd. | Activated carbon fiber spun yarn |
| CN1295142A (en) * | 2000-10-28 | 2001-05-16 | 中山大学 | Phosphoric acid activation process of producing active carbon fiber |
| CN1765489A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | Supported type active carbon and its preparation method |
| US20090048467A1 (en) * | 2007-08-13 | 2009-02-19 | Headwaters Technology Innovation, Llc | Methods for making immobilized aryl-containing ligands |
| CN101288820A (en) * | 2008-06-13 | 2008-10-22 | 北京云辰天环保科技有限公司 | Active carbon fiber organic gas recovery method and system using nitrogen as desorption medium |
| US20160361704A1 (en) * | 2012-04-25 | 2016-12-15 | Lg Chem, Ltd. | Super absorbent polymer and a preparation method thereof |
| CN203447939U (en) * | 2013-01-31 | 2014-02-26 | 东洋纺株式会社 | Gas processing device |
| CN104906917A (en) * | 2014-03-12 | 2015-09-16 | 北京日新达能技术有限公司 | Method for multistage adsorption and recovery of organic gases through active carbon fiber |
| CN106824267A (en) * | 2017-01-25 | 2017-06-13 | 江西省汉氏贵金属有限公司 | A kind of Suzuki coupling reactions palladium-carbon catalyst and preparation method thereof |
| CN107651651A (en) * | 2017-09-29 | 2018-02-02 | 浙江工业大学 | A kind of porosu solid supported ion liquid of absorption HCl gases |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115672271A (en) * | 2022-10-25 | 2023-02-03 | 山东格瑞德环保科技有限公司 | Modified activated carbon for oil gas recovery and preparation method thereof |
| CN115672271B (en) * | 2022-10-25 | 2023-12-15 | 山东格瑞德环保科技有限公司 | Modified activated carbon for oil gas recovery and preparation method thereof |
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