CN110755992A - Modified adsorbent and preparation method thereof - Google Patents
Modified adsorbent and preparation method thereof Download PDFInfo
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- CN110755992A CN110755992A CN201810844399.XA CN201810844399A CN110755992A CN 110755992 A CN110755992 A CN 110755992A CN 201810844399 A CN201810844399 A CN 201810844399A CN 110755992 A CN110755992 A CN 110755992A
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Abstract
A modified adsorbent and a preparation method thereof belong to the technical field of waste gas treatment. The method is characterized by comprising the following steps: the activated carbon fiber is modified by a compound of aryl phosphine or a derivative thereof and phosphoric acid or phosphate, wherein the mass ratio of the aryl phosphine or the derivative thereof to the phosphoric acid or phosphate is (0.18-6): 1. the preparation method comprises the following steps: 1) preparing an activating solution with the total mass concentration of 1-10% of the activating agent by taking a compound of aryl phosphine or a derivative thereof and phosphoric acid or phosphate as the activating agent and butanol as a solvent, and soaking the carbon fibers in the activating solution for 10-36 hours; 2) filtering, filtering to remove a butanol solution, heating and activating in inert gas at 120-200 ℃, and cooling to obtain the modified activated carbon fiber adsorbent. The adsorbent provided by the invention has high desorption efficiency, the active carbon fiber has long service life, and the problem of low octanol adsorption and desorption efficiency is fundamentally solved.
Description
Technical Field
A modified adsorbent and a preparation method thereof belong to the technical field of waste gas treatment.
Background
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 treatment of waste gas by using activated carbon fiber as adsorbent becomes a research hotspot of scholars at home and abroad in recent years. Different from organic pollutants such as ethanol, butanol, benzene, toluene and the like, the (iso) octanol brings great difficulty to the waste gas treatment due to the characteristics of high boiling point, large liquid viscosity and the like.
(Iso) octanol was a colorless transparent oily liquid having an irritant odor, a boiling point (normal atmospheric pressure) of 189 ℃ and a vapor pressure (20 ℃) of 66.66 Pa. (iso) 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 (iso) 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 also exists in the practical operation, the content of (iso) octanol cannot reach the national specified discharge standard in the loading tail gas and the direct exhaust of a production device, the recovery treatment is needed, and the problem that the waste gas pollutes the environment is fundamentally solved.
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 the organic pollutants with high boiling points is not involved.
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, and the formula of the activating agent is also different from the invention.
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, and the conventional organic pollutants with lower boiling points are treated, and the boiling points are about 100 ℃.
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 modified adsorbent with high adsorption efficiency and high temperature resistance and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: the modified adsorbent is characterized by comprising the following components: the activated carbon fiber is modified by a compound of aryl phosphine or a derivative thereof and phosphoric acid or phosphate, wherein the mass ratio of the aryl phosphine or the derivative thereof to the phosphoric acid or phosphate is (0.18-6): 1.
the modified adsorbent takes the activated carbon fiber as the adsorbent, and the activated carbon fiber is modified to carbonize the fiber and increase the specific surface area, so that the adsorption efficiency is improved; in the desorption process, the characteristic of azeotropy of (iso) octanol and water is utilized, the activated carbon fiber can be quickly and effectively desorbed and regenerated, the problems that the activated carbon fiber regeneration energy consumption is high and the emission standard is difficult to reach after (iso) octanol is adsorbed in waste gas due to low adsorption rate and high desorption temperature in the existing (iso) octanol adsorption technology are solved, and the use efficiency of the activated carbon fiber is improved.
Preferably, the activated carbon fiber is viscose-based activated carbon fiber, felt-like or sheet-like, and the specific surface area is 1010 m2/g~1090m2(ii) in terms of/g. The activated carbon fiber is preferably a commercially available activated carbon fiber of type T1300 which satisfies the above conditions.
Preferably, the aryl phosphine 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.
Preferably, the aryl phosphine 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 aryl phosphine derivative 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 phosphate is sodium dihydrogen phosphate, potassium dihydrogen phosphate or/and ammonium dihydrogen phosphate. The phosphate is preferably hydrogen phosphate, including monohydrogen phosphate and dihydrogen phosphate, preferably sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium dihydrogen phosphate.
Preferably, the mass ratio of the aryl phosphine or the derivative thereof to the phosphoric acid or the phosphate 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 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.
The preparation method of the modified adsorbent is characterized by comprising the following steps:
1) preparing an activating solution with the total mass concentration of 1-10% of the activating agent by taking a compound of aryl phosphine or a derivative thereof and phosphoric acid or phosphate as the activating agent and butanol as a solvent, and soaking the carbon fibers in the activating solution for 10-36 hours;
2) filtering, filtering to remove a butanol solution, heating and activating in inert gas at 120-200 ℃, and cooling to obtain the modified activated carbon fiber adsorbent.
In the preparation method, the specific surface is enlarged through impregnation and fiber activation, and the adsorbent is endowed with stronger adsorption force.
Preferably, the total mass concentration of the activating agent in butanol is 2-6%. The preferred 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.
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 completion of the impregnation, filtration was carried out.
In the step 2), activation is carried out in an inert gas environment, wherein the inert gas is nitrogen or argon, and the activation 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.
The application of the modified adsorbent in the treatment of the pollution of the waste gas is used for treating the (iso) octanol waste gas with high boiling point, and comprises the following steps:
(1) loading the modified adsorbent into an adsorber; the adsorption device comprises 3 adsorbers, one adsorber is always kept for adsorption, one adsorber is always kept for drying, one adsorber is always kept for desorption after saturation, and the operation is switched; the gas containing (iso) octanol firstly enters an adsorber A in an adsorption state for adsorption, the (iso) octanol 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 sent into an adsorber B for cooling and drying, and meanwhile, secondary adsorption is carried out, so that the tail gas after adsorption is ensured to be qualified and is discharged into the atmosphere;
(2) while the adsorption is carried out, a water entrainer is injected into the adsorber C in an adsorption saturation state to allow the (iso) octanol to be desorbed from the water in an azeotropic manner. Then low-pressure steam enters the adsorber C, and the adsorber C 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 organic (iso) octanol, and the lower layer liquid is azeotropic water. The azeotropic water is used as azeotropic agent and returns to the absorber C for recycling, and after the (iso) octanol reaches a certain height, the azeotropic water overflows into the metering tank to be recovered as a product.
In the step (1), the modified adsorbent is filled into an adsorber, the adsorption of (iso) octanol waste gas is switched among 3 adsorbers, the waste gas firstly enters an adsorber A in an adsorption state from the bottom, the (iso) octanol gas is adsorbed by activated carbon fibers and flows out from the top of an adsorption bed layer, the separation of organic components in the waste gas from air is an important characteristic of the activated carbon fiber adsorber, the (iso) octanol at the outlet of the adsorber is reduced to a lower state by the adsorption of the bed layer of the adsorber A, and the (iso) octanol 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 A is mixed with air to form enough gas volume, and the gas is used as a drying gas source to enter the adsorption bed B after desorption, and exhaust steam of low-pressure steam is blown out to play a role in cooling; meanwhile, for the (iso) octanol waste gas, the (iso) octanol which is not completely adsorbed by the adsorber A can be subjected to secondary adsorption, and the content of the (iso) octanol in the tail gas after adsorption can be ensured to be lower than the national emission requirement through the process. Wherein, the mixing proportion of the (iso) octanol-containing waste gas and the dry air is waste gas: air (V/V) = 1-6: 1.
When an adsorbent bed 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 (iso) octanol, and the desorption effect is good.
In the step (2), because the boiling point of (iso) octanol is 189 ℃, the (iso) octanol is generally heated to 200 ℃ during desorption and is difficult to remove. The (iso) octanol and water can form an azeotrope, the azeotropic composition contains 20 percent of water and the azeotropic point is 99.1 ℃. The water is used as the entrainer, so that the desorption difficulty can be effectively reduced, the desorption efficiency is improved, and the purposes of saving energy, reducing consumption, improving the desorption effect and prolonging the service life of the adsorbent are achieved. The dosage of the entrainer is 22 to 25 percent of the adsorption quantity of the (iso) octanol. The (iso) octanol can be desorbed by low-pressure steam at 100 ℃.
In the step (3), the mixed steam containing (iso) octanol generated by desorption enters a condenser for condensation, and the cooling medium is cooling water. 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 (iso) octanol from the water. The azeotropic water is used as azeotropic agent and returns to the absorber C for recycling, and the (iso) 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: compared with the adsorbent and the process effect in the prior art, the modified adsorbent and the preparation method thereof have the advantages that the formula of the aryl phosphine or the derivative thereof and the activating agent of phosphoric acid or phosphate is adopted in the modification process of the adsorbent, and the specific surface is enlarged through impregnation and fiber activation, so that the adsorbent is endowed with stronger adsorption force; when in use, two-stage adsorption can be adopted, wherein the first stage adopts jacket internal circulation cooling for taking away adsorption heat in time, thereby effectively improving the recovery rate of (iso) octanol and eliminating the phenomenon of adsorption heat accumulation; the second adsorption plays a role in cooling, and simultaneously, the content of (iso) octanol in the tail gas after adsorption can be ensured to be lower than the national emission requirement. In the desorption process, water can be used as an entrainer, the desorption temperature is reduced from 200 ℃ to 100 ℃, the desorption rate is improved, the service life of the adsorbent is prolonged, the whole process operation has the characteristics of high adsorption and desorption efficiency, low energy consumption, safety and reliability, and the safe adsorption of the (iso) octanol waste gas with high boiling point and high concentration is realized.
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 12 h, 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 shown in the experimental data in Table 1, compared with comparative example 1, the carbon fiber has a significantly increased specific surface area after modification, from 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 4 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 4 were 3.5mm thick before the first loading into the adsorber.
The data in table 3 show that the carbon fiber of comparative example 4 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 modified adsorbent, characterized by comprising: the activated carbon fiber is modified by a compound of aryl phosphine or a derivative thereof and phosphoric acid or phosphate, wherein the mass ratio of the aryl phosphine or the derivative thereof to the phosphoric acid or phosphate is (0.18-6): 1.
2. the modified adsorbent of claim 1, wherein: the activated carbon fiber is viscose-based activated carbon fiber, felt-shaped or flaky, and the specific surface area is 1010 m2/g ~1090m2/g。
3. The modified adsorbent of claim 1, wherein: the aryl phosphine is triphenylphosphine, triphenylphosphine oxide, diphenyl phosphine, alkyl diphenyl phosphine or/and tri-o-tolyl phosphine.
4. The modified adsorbent of claim 1, wherein: the aryl phosphine is triphenylphosphine.
5. The modified adsorbent of claim 1, wherein: the aryl phosphine derivative is ethoxycarbonyl ethylidene triphenylphosphine, methoxyformyl ethylidene triphenylphosphine, ethoxyformyl methylene triphenylphosphine or/and methoxyformyl methylene triphenylphosphine.
6. The modified adsorbent of claim 1, wherein: the phosphate is sodium dihydrogen phosphate, potassium dihydrogen phosphate or/and ammonium dihydrogen phosphate.
7. The modified adsorbent of claim 1, wherein: the mass ratio of the aryl phosphine or the derivative thereof to the phosphoric acid or the phosphate is 0.25-4: 1.
8. The modified adsorbent of claim 1, wherein: the mass ratio of the aryl phosphine or the derivative thereof to the phosphoric acid or the phosphate is 0.5-3: 1.
9. The method for preparing the modified adsorbent according to any one of claims 1 to 8, characterized by comprising the steps of:
1) preparing an activating solution with the total mass concentration of 1-10% of the activating agent by taking a compound of aryl phosphine or a derivative thereof and phosphoric acid or phosphate as the activating agent and butanol as a solvent, and soaking the carbon fibers in the activating solution for 10-36 hours;
2) filtering, filtering to remove a butanol solution, heating and activating in inert gas at 120-200 ℃, and cooling to obtain the modified activated carbon fiber adsorbent.
10. The method for preparing a modified adsorbent according to claim 9, wherein: the total mass concentration of the activating agent in butanol is 2-6%.
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