CN110975523A - Method for recovering n-butane in tail gas generated in preparation of maleic anhydride by butane method - Google Patents
Method for recovering n-butane in tail gas generated in preparation of maleic anhydride by butane method Download PDFInfo
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Abstract
The invention discloses a method for recovering n-butane in tail gas generated in the preparation of maleic anhydride by a butane method, which comprises the following steps: firstly, pressurizing tail gas of maleic anhydride preparation by a butane method, and feeding the tail gas into a spray washer to wash and spray; secondly, sending the tail gas of butane-process maleic anhydride sprayed by washing into an adsorber to selectively adsorb with an adsorbent to obtain the adsorbent for adsorbing n-butane; thirdly, feeding the adsorbent for adsorbing the n-butane into a regenerator to react with water vapor for regeneration to obtain n-butane-rich gas and a regenerated adsorbent; fourthly, sending the n-butane-rich gas into a condensation tank for cooling and separating to obtain n-butane and water; fifthly, the regenerated adsorbent is recycled. The method adopts the adsorbent to selectively adsorb the maleic anhydride tail gas prepared by the butane method, effectively removes impurity gases, and obtains the n-butane through regeneration and cooling separation, thereby realizing continuous and efficient recovery of the n-butane in the maleic anhydride tail gas prepared by the butane method, improving the recovery rate and quality of the n-butane, and simultaneously improving the utilization rate of the n-butane in the maleic anhydride tail gas prepared by the butane method.
Description
Technical Field
The invention belongs to the technical field of tail gas recovery, and particularly relates to a method for recovering normal butane in tail gas generated in a butane method for preparing maleic anhydride.
Background
Maleic anhydride is called maleic anhydride for short, and has wide application and gradually increased demand year by year. The industrial production of maleic anhydride in China is gradually changed from benzene oxidation with serious pollution to n-butane oxidation.
The butane method for preparing maleic anhydride is to mix n-butane and air and then to react in a reactor to generate maleic anhydride, water, CO and CO2The reaction process of (1). In the normal course of production, only 82% of the n-butane conversion and also 18% of the n-butane is left unreacted in the offgas. How to improve the yield and utilization rate of the n-butane is the research focus of scholars. If the n-butane in the tail gas is recycled, the yield of the maleic anhydride can be increased by about 15-18% on the basis of unchanged raw material cost of the n-butane. Therefore, the research on suitable n-butane recovery technology is the development direction of maleic anhydride tail gas treatment technology.
The tail gas treatment mode adopted in the industrial production of preparing maleic anhydride by a butane method mainly comprises the following steps: heat accumulating combustion, catalytic combustion and partial tail gas circulation technology. Wherein, the heat accumulating type combustion and the catalytic combustion are adopted by most maleic anhydride enterprises in China.
Patent application publication No. CN 109974015A discloses a waste gas treatment process by which n-butane and carbon monoxide in maleic anhydride tail gas are completely oxidized into carbon dioxide and water by a thermal storage incineration method. The process is adopted to treat the tail gas, the n-butane in the tail gas is not recovered at all, the n-butane is only used as a fuel, the resource waste is caused, and the CO is increased2Emissions, while also presenting NOx emissions issues.
Patent application publication No. CN 206291222U discloses a waste gas treatment device for n-butane production, which adopts a catalytic combustion furnace to completely oxidize n-butane and carbon monoxide in maleic anhydride tail gas into carbon dioxide and water by a catalytic incineration method. The tail gas treatment by adopting the process reduces the emission of NOx, but the recycling of the n-butane in the tail gas cannot be realized.
Petrochemical technology and application, reported in 2014, volume 32, No. 1, the cycle of tail gas in the maleic anhydride production process by the n-butane oxidation method, and introduced a part of tail gas cycle process technology and application of the same of the company CONSER in Italy. The maleic anhydride tail gas is divided into 2 paths: (1) separating impurities such as solvent, acrylic acid, acetic acid, water and the like carried in the tail gas of the reaction absorption tower from 40 percent of tail gas through the working procedures of cooling, separating, washing and the like, then entering a second-stage inlet of an air compressor, and circularly entering a reactor; (2) and sending the residual 60 percent of tail gas to an incinerator for incineration, thereby realizing the partial recycling of the tail gas. Limited by the proportion of raw materials, the process can only recycle 40% of tail gas, the recovery rate of n-butane in the tail gas is only 40%, and the processes of separation, washing and the like are required to be added, so that the equipment investment cost is higher.
The application publication No. CN 106669376A discloses a method for utilizing butane oxidation tail gas, which comprises the steps of firstly carrying out dehydration and dust removal treatment on maleic anhydride tail gas, and separating the treated tail gas by using a membrane reactor. The method utilizes a cellulose acetate membrane to remove impurities such as carbon monoxide, propionic acid, acetic acid, solvent, water and the like in tail gas generated in the preparation of maleic anhydride by oxidizing n-butane, and separates out mixed gas of n-butane and nitrogen for recycling. The method can recover the n-butane in the tail gas, but the n-butane and the nitrogen in the recovered gas are not separated, and the maleic anhydride production can be realized only by ensuring the composition of raw material gas for maleic anhydride production by additionally adding control equipment, so that the process is complex and the operation difficulty is high.
Researchers have done a lot of related work, but as mentioned above, the existing technology for treating tail gas generated in the preparation of maleic anhydride by butane method has the following disadvantages: (1) the n-butane in the maleic anhydride tail gas is not recovered or partially recovered; (2) other gases can not be completely separated while the normal butane is recovered, and the gases which can not be separated are circularly introduced into the maleic anhydride production raw material, so that the original process conditions for producing the maleic anhydride are changed, and the adverse effect on a maleic anhydride production system can be caused; (3) and the addition of precise gas component analysis and control equipment makes the process complicated and increases the operation difficulty and equipment investment.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for recovering n-butane in tail gas of maleic anhydride prepared by a butane method aiming at the defects of the prior art. The method adopts the adsorbent to selectively adsorb the tail gas of the maleic anhydride prepared by the butane method, effectively removes impurity gas in the tail gas of the maleic anhydride prepared by the butane method, then obtains n-butane through regeneration and cooling separation in sequence, and the regenerated adsorbent can be used for cyclic selective adsorption, thereby realizing continuous and efficient recovery of the n-butane in the tail gas of the maleic anhydride prepared by the butane method, improving the recovery rate and quality of the n-butane and simultaneously improving the utilization rate of the n-butane in the tail gas of the maleic anhydride prepared by the butane method.
In order to solve the technical problems, the invention adopts the technical scheme that: a method for recovering n-butane in tail gas generated in a butane process for preparing maleic anhydride is characterized by comprising the following steps:
step one, pressurizing the tail gas of the butane method maleic anhydride by using a gas booster and sending the tail gas into a spray scrubber for water washing and spraying;
step two, sending the tail gas of the butane-process maleic anhydride sprayed by water washing in the step one into an adsorber through a first gas inlet to selectively adsorb with an adsorbent entering the adsorber through a first feed inlet to obtain an adsorbent adsorbing n-butane and adsorbed tail gas, and then discharging the adsorbed tail gas through a first gas outlet to enter an incinerator to be incinerated and removed; the adsorbent flows from top to bottom in the adsorber in a plug flow state, and the flow direction of the adsorbent is opposite to the movement and discharge direction of the adsorbed tail gas;
step three, the adsorbent for adsorbing the n-butane obtained in the step two enters a screw propeller through a first discharge hole, then enters a regenerator through a second feed hole downwards, is regenerated under the action of water vapor entering the regenerator through a second air inlet to obtain n-butane-rich gas and a regenerated adsorbent, and then the regenerated adsorbent is sent into a riser through a second discharge hole; the adsorbent for adsorbing the n-butane flows from top to bottom in the regenerator in a horizontal plug flow state, and the flow direction of the adsorbent for adsorbing the n-butane is opposite to the flow direction of the movement of the water vapor;
step four, discharging the n-butane-rich gas obtained in the step three through a second gas outlet, sending the gas into a condensation tank for cooling and separation to obtain n-butane and water, sending the n-butane into the n-butane tank for storage, and sending the water into a water tank for storage;
and step five, feeding the regenerated adsorbent obtained in the step three into an adsorber through a first feed inlet, and then continuing to perform the selective adsorption process of the step two, the regeneration process of the step three and the cooling separation process of the step four to continuously recover the n-butane in the tail gas of the maleic anhydride preparation by the butane method.
The adsorbent is adopted to selectively adsorb the butane method maleic anhydride tail gas to obtain the adsorbent for adsorbing n-butane, so that impurity gas in the butane method maleic anhydride tail gas is effectively removed, the adsorbent is regenerated under the action of water vapor to obtain n-butane-rich gas, the adsorbent is regenerated at the same time, the n-butane-rich gas is cooled and separated to obtain n-butane and water, the efficient recovery of the n-butane in the butane method maleic anhydride tail gas is realized, the adverse effect of the impurity gas in the butane method maleic anhydride tail gas is avoided, the purity of the recovered n-butane is high, the n-butane adsorption process and the regeneration desorption process in the process both simulate a moving bed reactor, the process is simple, the requirement on equipment is low, the implementation is easy, and the application value is excellent; in addition, the regenerated adsorbent is subjected to cyclic selective adsorption, so that the continuous recovery of the n-butane in the tail gas of the maleic anhydride preparation by the butane method is realized, the recovery cost is reduced, the waste is avoided, the introduction of new impurities is avoided, and the quality of the n-butane is improved.
The method for recovering the n-butane in the tail gas of the maleic anhydride prepared by the butane method is characterized in that in the first step, the tail gas of the maleic anhydride prepared by the butane method consists of the following gas components in percentage by volume: n-butane 0.1-0.5%, carbon monoxide 0.5-2.0%, carbon dioxide 0.5-2.0%, oxygen 8-20%, and nitrogen in balance. The composition is the composition of most of tail gas generated in the preparation of maleic anhydride by a butane method, and the applicability of the recovery method is improved.
The method for recovering the n-butane in the tail gas generated in the preparation of the maleic anhydride by the butane method is characterized in that the pressure after pressurization in the first step is 100 kPa-500 kPa. Within this pressure range, it is possible to ensure that the adsorption of n-butane is carried out, and although the adsorption of n-butane is favored by an increase in pressure, an increase in pressure markedly increases the energy consumption, and the pressure is preferably from 100kPa to 500kPa in view of the combination.
The method for recovering the n-butane in the tail gas generated in the preparation of the maleic anhydride by the butane method is characterized in that the water temperature adopted in the water washing and spraying in the first step is 10-50 ℃. The temperature of the water in the range belongs to the normal temperature range, is easy to realize, does not need to carry out strict temperature control, and is convenient to operate.
The method for recovering the n-butane in the tail gas generated in the preparation of the maleic anhydride by the butane method is characterized in that the adsorbent in the second step is a molecular sieve, a modified molecular sieve or a resin adsorbent, and the adsorbent is a spherical adsorbent. The adsorbent is further preferably a 13X molecular sieve, a modified styrene polymer resin, a 5A molecular sieve and a modified 5A molecular sieve, and the adsorbent has a developed pore structure and a large specific surface area, is easy to adsorb n-butane and desorb, and effectively exerts the selective adsorption performance; the adsorbent is further preferably a spherical adsorbent with the diameter of 1 mm-6 mm, so that the adsorbent not only has good fluidity, but also avoids overlarge pressure drop of adsorbed gas and ensures uniform distribution of fluid.
The method for recovering the n-butane in the tail gas of the maleic anhydride preparation by the butane method is characterized in that the pressure of the water vapor in the third step is 110 kPa-510 kPa. The effect of desorbing the n-butane by using the water vapor in the pressure range is good.
The method for recovering the n-butane in the tail gas generated in the preparation of the maleic anhydride by the butane method is characterized in that the temperature of the condensation tank in the fourth step is 10-40 ℃. Good separation of n-butane and water is ensured in this temperature range.
Compared with the prior art, the invention has the following advantages:
1. the method adopts the adsorbent to selectively adsorb the tail gas of the maleic anhydride prepared by the butane method, effectively removes impurity gases in the tail gas of the maleic anhydride prepared by the butane method, and then obtains the n-butane through regeneration and cooling separation in sequence, and the regenerated adsorbent can be used for circular selective adsorption, thereby realizing continuous and efficient recovery of the n-butane in the tail gas of the maleic anhydride prepared by the butane method, improving the recovery rate and quality of the n-butane and simultaneously improving the utilization rate of the n-butane in the tail gas of the maleic anhydride prepared by the butane method.
2. The invention adopts the adsorbent to carry out solid-gas phase selective adsorption on the tail gas of the maleic anhydride prepared by the butane method, avoids the adverse effect of impurity gas in the tail gas of the maleic anhydride prepared by the butane method, obtains the n-butane with higher purity and better quality, can be directly applied to raw materials for producing the maleic anhydride, does not need to change the original production process, and has no adverse effect on a maleic anhydride production system.
3. The normal butane adsorption process and the regenerative desorption process in the invention are both simulated moving bed reactors, the process is simple, the operation process is stable, the requirement on equipment is low, precise gas analysis control equipment is not required to be added, the recovery cost is reduced, and the practical value of the recovery method is improved.
4. The regeneration of the adsorbent is realized in the recovery process, and the regenerated adsorbent can be continuously used for selective adsorption in the recovery process, so that the recovery cost is further reduced.
5. In the recovery process of the invention, no harmful reagent or medicine is adopted, and the products in each step are safe and nontoxic, do not pollute the environment, and are green and environment-friendly.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is a schematic view of the recovery apparatus of the present invention.
FIG. 2 is a schematic view showing the connection structure of the screw propeller, the adsorber and the regenerator in the recovery apparatus according to the present invention.
Description of the reference numerals
1-an adsorber; 1-1 — a first feed port; 1-2-a first outlet;
1-3 — a first gas inlet; 1-4-a first discharge port; 2-screw propeller;
2-1-a rate-controlling electrode; 2-pushing screw; 2-3-screw propeller outlet
3-a regenerator; 3-1-second feed inlet; 3-2-second outlet;
3-3 — a second gas inlet; 3-4-a second discharge port; 4-spray washer;
5, a gas booster; 6, a riser; 7-condensation tank;
8-n-butane tank; 9-water tank.
Detailed Description
As shown in figure 1, the activation device of the invention comprises an absorber 1 and a regenerator 3 connected with the absorber 1 through a screw propeller 2, wherein the top and the bottom of the absorber 1 are respectively and correspondingly provided with a first feed inlet 1-1 and a first discharge outlet 1-4, the upper side surface of the absorber 1 is provided with a first gas outlet 1-2, the lower side surface is provided with a first gas inlet 1-3, the first gas inlet 1-3 is sequentially connected with a spray scrubber 4 and a gas supercharging 5, the top and the bottom of the regenerator 3 are respectively and correspondingly provided with a second feed inlet 3-1 and a second discharge outlet 3-4, the second discharge outlet 3-4 is connected with a riser 6, the riser 6 is connected with the first feed inlet 1-1, the upper side surface of the regenerator 3 is provided with a second gas outlet 3-2, the side surface of the lower part of the device is provided with a second air inlet 3-3, the second air outlet 3-2 is connected with a condensing tank 7, the air outlet of the condensing tank 7 is connected with an n-butane tank 8, and the liquid outlet of the condensing tank 7 is connected with a water tank 9.
As shown in figure 2, a screw propeller 2 in the recovery device comprises a propelling screw 2-2 and a speed control motor 2-1 connected with the propelling screw 2-2, a first discharge port 1-4 of an absorber 1 is vertical to the propelling screw, a screw propeller outlet 2-3 is arranged at one end of the screw propeller 2 far away from the first discharge port 1-4, and a second feed port 3-1 of a regenerator 3 is vertical to the screw propeller outlet 2-3.
Example 1
The method of the embodiment comprises the following steps:
step one, pressurizing the tail gas of the butane method maleic anhydride to 100kPa by using a gas booster 5, and feeding the tail gas into a spray washer 4 for water washing and spraying; the tail gas of the butane method maleic anhydride is composed of the following gas components in percentage by volume: n-butane 0.1%, carbon monoxide 2%, carbon dioxide 2%, oxygen 8%, and nitrogen in balance; the water temperature adopted by the water washing spraying is 10 ℃;
step two, sending the tail gas of the butane-process maleic anhydride sprayed by water washing in the step one into an adsorber 1 through a first gas inlet 1-3 to selectively adsorb with an adsorbent entering the adsorber 1 through a first feed inlet 1-1 to obtain an adsorbent adsorbing n-butane and adsorbed tail gas, and then discharging the adsorbed tail gas through a first gas outlet 1-2 to enter an incinerator to be incinerated and removed; the adsorbent flows from top to bottom in the adsorber 1 in a plug flow state, and the flow direction of the adsorbent is opposite to the movement and discharge direction of the adsorbed tail gas; the adsorbent is a spherical 13X molecular sieve adsorbent with the diameter of 1 mm;
step three, the adsorbent for adsorbing the n-butane obtained in the step two enters a screw propeller 2 through a first discharge port 1-4, then enters a regenerator 3 through a second feed port 3-1 downwards, is regenerated under the action of water vapor entering the regenerator 3 through a second air inlet 3-3 to obtain n-butane-rich gas and a regenerated adsorbent, and then the regenerated adsorbent is sent into a riser 6 through a second discharge port 3-4; the adsorbent for adsorbing the n-butane flows from top to bottom in the regenerator 3 in a plug flow state, and the flow direction of the adsorbent for adsorbing the n-butane is opposite to the flow direction of the movement of the water vapor; the pressure of the water vapor is 110 kPa;
step four, discharging the n-butane-rich gas obtained in the step three through a second gas outlet 3-2, then sending the gas into a condensation tank 7 with the temperature of 10 ℃ for cooling and separation to obtain n-butane and water, sending the n-butane into a n-butane tank 8 for storage, and sending the water into a water tank 9 for storage;
and step five, feeding the regenerated adsorbent obtained in the step three into an adsorber 1 through a first feed port 1-1, and then continuing to perform the selective adsorption process in the step two, the regeneration process in the step three and the cooling separation process in the step four to continuously recover the n-butane in the tail gas of the maleic anhydride preparation by the butane method.
Example 2
The method of the embodiment comprises the following steps:
step one, pressurizing the tail gas of the butane method maleic anhydride to 500kPa by using a gas booster 5, and feeding the tail gas into a spray washer 4 for water washing and spraying; the tail gas of the butane method maleic anhydride is composed of the following gas components in percentage by volume: n-butane 0.5%, carbon monoxide 0.5%, carbon dioxide 0.5%, oxygen 20%, and nitrogen in balance; the water temperature adopted by the water washing spraying is 50 ℃;
step two, sending the tail gas of the butane-process maleic anhydride sprayed by water washing in the step one into an adsorber 1 through a first gas inlet 1-3 to selectively adsorb with an adsorbent entering the adsorber 1 through a first feed inlet 1-1 to obtain an adsorbent adsorbing n-butane and adsorbed tail gas, and then discharging the adsorbed tail gas through a first gas outlet 1-2 to enter an incinerator to be incinerated and removed; the adsorbent flows from top to bottom in the adsorber 1 in a plug flow state, and the flow direction of the adsorbent is opposite to the movement and discharge direction of the adsorbed tail gas; the adsorbent is a spherical resin adsorbent with the diameter of 6 mm;
step three, the adsorbent for adsorbing the n-butane obtained in the step two enters a screw propeller 2 through a first discharge port 1-4, then enters a regenerator 3 through a second feed port 3-1 downwards, is regenerated under the action of water vapor entering the regenerator 3 through a second air inlet 3-3 to obtain n-butane-rich gas and a regenerated adsorbent, and then the regenerated adsorbent is sent into a riser 6 through a second discharge port 3-4; the adsorbent for adsorbing the n-butane flows from top to bottom in the regenerator 3 in a plug flow state, and the flow direction of the adsorbent for adsorbing the n-butane is opposite to the flow direction of the movement of the water vapor; the pressure of the water vapor is 510 kPa;
step four, discharging the n-butane-rich gas obtained in the step three through a second gas outlet 3-2, then sending the gas into a condensation tank 7 with the temperature of 40 ℃ for cooling and separation to obtain n-butane and water, sending the n-butane into a n-butane tank 8 for storage, and sending the water into a water tank 9 for storage;
and step five, feeding the regenerated adsorbent obtained in the step three into an adsorber 1 through a first feed port 1-1, and then continuing to perform the selective adsorption process in the step two, the regeneration process in the step three and the cooling separation process in the step four to continuously recover the n-butane in the tail gas of the maleic anhydride preparation by the butane method.
Example 3
The method of the embodiment comprises the following steps:
step one, pressurizing the tail gas of the butane method maleic anhydride to 250kPa by using a gas booster 5, and feeding the tail gas into a spray washer 4 for water washing and spraying; the tail gas of the butane method maleic anhydride is composed of the following gas components in percentage by volume: n-butane 0.2%, carbon monoxide 1.1%, carbon dioxide 1.0%, oxygen 14%, and nitrogen in balance; the water temperature adopted by the water washing spraying is 15 ℃;
step two, sending the tail gas of the butane-process maleic anhydride sprayed by water washing in the step one into an adsorber 1 through a first gas inlet 1-3, and selectively adsorbing the tail gas with an adsorbent entering the adsorber 1 through a first feed inlet 1-1 to obtain an adsorbent for adsorbing n-butane and adsorption tail gas; the adsorbent flows from top to bottom in the adsorber 1 in a horizontal plug flow state, and the flow direction of the adsorbent is opposite to the movement and discharge direction of the adsorbed tail gas; the adsorbent is a spherical Ca modified 5A molecular sieve adsorbent with the diameter of 2 mm;
step three, the adsorbent for adsorbing the n-butane obtained in the step two enters a screw propeller 2 through a first discharge port 1-4, then enters a regenerator 3 through a second feed port 3-1 downwards, is regenerated under the action of water vapor entering the regenerator 3 through a second air inlet 3-3 to obtain n-butane-rich gas and a regenerated adsorbent, and then the regenerated adsorbent is sent into a riser 6 through a second discharge port 3-4; the adsorbent for adsorbing the n-butane flows from top to bottom in the regenerator 3 in a plug flow state, and the flow direction of the adsorbent for adsorbing the n-butane is opposite to the flow direction of the movement of the water vapor; the pressure of the water vapor is 270 kPa;
step four, discharging the n-butane-rich gas obtained in the step three through a second gas outlet 3-2, then sending the gas into a condensation tank 7 with the temperature of 15 ℃ for cooling and separation to obtain n-butane and water, sending the n-butane into a n-butane tank 8 for storage, and sending the water into a water tank 9 for storage;
and step five, feeding the regenerated adsorbent obtained in the step three into an adsorber 1 through a first feed port 1-1, and then continuing to perform the selective adsorption process in the step two, the regeneration process in the step three and the cooling separation process in the step four to continuously recover the n-butane in the tail gas of the maleic anhydride preparation by the butane method.
Example 4
The method of the embodiment comprises the following steps:
step one, pressurizing the tail gas of the butane method maleic anhydride to 350kPa by using a gas booster 5, and feeding the tail gas into a spray washer 4 for water washing and spraying; the tail gas of the butane method maleic anhydride is composed of the following gas components in percentage by volume: n-butane 0.3%, carbon monoxide 0.9%, carbon dioxide 1.1%, oxygen 13%, and nitrogen in balance; the water temperature adopted by the water washing spraying is 20 ℃;
step two, sending the tail gas of the butane-process maleic anhydride sprayed by water washing in the step one into an adsorber 1 through a first gas inlet 1-3 to selectively adsorb with an adsorbent entering the adsorber 1 through a first feed inlet 1-1 to obtain an adsorbent adsorbing n-butane and adsorbed tail gas, and then discharging the adsorbed tail gas through a first gas outlet 1-2 to enter an incinerator to be incinerated and removed; the adsorbent flows from top to bottom in the adsorber 1 in a plug flow state, and the flow direction of the adsorbent is opposite to the movement and discharge direction of the adsorbed tail gas; the adsorbent is a spherical resin adsorbent with the diameter of 3 mm;
step three, the adsorbent for adsorbing the n-butane obtained in the step two enters a screw propeller 2 through a first discharge port 1-4, then enters a regenerator 3 through a second feed port 3-1 downwards, is regenerated under the action of water vapor entering the regenerator 3 through a second air inlet 3-3 to obtain n-butane-rich gas and a regenerated adsorbent, and then the regenerated adsorbent is sent into a riser 6 through a second discharge port 3-4; the adsorbent for adsorbing the n-butane flows from top to bottom in the regenerator 3 in a plug flow state, and the flow direction of the adsorbent for adsorbing the n-butane is opposite to the flow direction of the movement of the water vapor; the pressure of the water vapor is 360 kPa;
step four, discharging the n-butane-rich gas obtained in the step three through a second gas outlet 3-2, then sending the gas into a condensation tank 7 with the temperature of 20 ℃ for cooling and separation to obtain n-butane and water, sending the n-butane into a n-butane tank 8 for storage, and sending the water into a water tank 9 for storage;
and step five, feeding the regenerated adsorbent obtained in the step three into an adsorber 1 through a first feed port 1-1, and then continuing to perform the selective adsorption process in the step two, the regeneration process in the step three and the cooling separation process in the step four to continuously recover the n-butane in the tail gas of the maleic anhydride preparation by the butane method.
Example 5
The method of the embodiment comprises the following steps:
step one, pressurizing the tail gas of the butane method maleic anhydride to 290kPa by using a gas booster 5, and feeding the tail gas into a spray washer 4 for water washing and spraying; the tail gas of the butane method maleic anhydride is composed of the following gas components in percentage by volume: n-butane 0.2%, carbon monoxide 1.1%, carbon dioxide 1.3%, oxygen 12%, and nitrogen in balance; the water temperature adopted by the water washing spraying is 18 ℃;
step two, sending the tail gas of the butane-process maleic anhydride sprayed by water washing in the step one into an adsorber 1 through a first gas inlet 1-3 to selectively adsorb with an adsorbent entering the adsorber 1 through a first feed inlet 1-1 to obtain an adsorbent adsorbing n-butane and adsorbed tail gas, and then discharging the adsorbed tail gas through a first gas outlet 1-2 to enter an incinerator to be incinerated and removed; the adsorbent flows from top to bottom in the adsorber 1 in a plug flow state, and the flow direction of the adsorbent is opposite to the movement and discharge direction of the adsorbed tail gas; the adsorbent is a spherical 5A type molecular sieve adsorbent with the diameter of 4 mm;
step three, the adsorbent for adsorbing the n-butane obtained in the step two enters a screw propeller 2 through a first discharge port 1-4, then enters a regenerator 3 through a second feed port 3-1 downwards, is regenerated under the action of water vapor entering the regenerator 3 through a second air inlet 3-3 to obtain n-butane-rich gas and a regenerated adsorbent, and then the regenerated adsorbent is sent into a riser 6 through a second discharge port 3-4; the adsorbent for adsorbing the n-butane flows from top to bottom in the regenerator 3 in a plug flow state, and the flow direction of the adsorbent for adsorbing the n-butane is opposite to the flow direction of the movement of the water vapor; the pressure of the water vapor is 310 kPa;
step four, discharging the n-butane-rich gas obtained in the step three through a second gas outlet 3-2, then sending the gas into a condensation tank 7 with the temperature of 19 ℃ for cooling and separation to obtain n-butane and water, sending the n-butane into a n-butane tank 8 for storage, and sending the water into a water tank 9 for storage;
and step five, feeding the regenerated adsorbent obtained in the step three into an adsorber 1 through a first feed port 1-1, and then continuing to perform the selective adsorption process in the step two, the regeneration process in the step three and the cooling separation process in the step four to continuously recover the n-butane in the tail gas of the maleic anhydride preparation by the butane method.
Example 6
The method of the embodiment comprises the following steps:
step one, pressurizing tail gas of a butane method maleic anhydride to 320kPa by using a gas booster 5, and feeding the tail gas into a spray washer 4 for water washing and spraying; the tail gas of the butane method maleic anhydride is composed of the following gas components in percentage by volume: n-butane 0.4%, carbon monoxide 1.0%, carbon dioxide 0.9%, oxygen 14%, and nitrogen in balance; the water temperature adopted by the water washing spraying is 17 ℃;
step two, sending the tail gas of the butane-process maleic anhydride sprayed by water washing in the step one into an adsorber 1 through a first gas inlet 1-3 to selectively adsorb with an adsorbent entering the adsorber 1 through a first feed inlet 1-1 to obtain an adsorbent adsorbing n-butane and adsorbed tail gas, and then discharging the adsorbed tail gas through a first gas outlet 1-2 to enter an incinerator to be incinerated and removed; the adsorbent flows from top to bottom in the adsorber 1 in a plug flow state, and the flow direction of the adsorbent is opposite to the movement and discharge direction of the adsorbed tail gas; the adsorbent is a spherical resin adsorbent with the diameter of 2 mm;
step three, the adsorbent for adsorbing the n-butane obtained in the step two enters a screw propeller 2 through a first discharge port 1-4, then enters a regenerator 3 through a second feed port 3-1 downwards, is regenerated under the action of water vapor entering the regenerator 3 through a second air inlet 3-3 to obtain n-butane-rich gas and a regenerated adsorbent, and then the regenerated adsorbent is sent into a riser 6 through a second discharge port 3-4; the adsorbent for adsorbing the n-butane flows from top to bottom in the regenerator 3 in a plug flow state, and the flow direction of the adsorbent for adsorbing the n-butane is opposite to the flow direction of the movement of the water vapor; the pressure of the water vapor is 330 kPa;
step four, discharging the n-butane-rich gas obtained in the step three through a second gas outlet 3-2, then sending the gas into a condensation tank 7 with the temperature of 16 ℃ for cooling and separation to obtain n-butane and water, sending the n-butane into a n-butane tank 8 for storage, and sending the water into a water tank 9 for storage;
and step five, feeding the regenerated adsorbent obtained in the step three into an adsorber 1 through a first feed port 1-1, and then continuing to perform the selective adsorption process in the step two, the regeneration process in the step three and the cooling separation process in the step four to continuously recover the n-butane in the tail gas of the maleic anhydride preparation by the butane method.
The volume percentage content of the tail gas (raw material tail gas) from the butane process for preparing maleic anhydride and the n-butane in the adsorption tail gas in the embodiments 1 to 6 of the present invention were measured, and the recovery rate of n-butane was calculated, and the results are shown in table 1 below. Wherein, the calculation formula of the n-butane recovery rate is as follows:
molar n-butane-gas volume x n-butane volume percent/22.4 flowing through the adsorber per unit time
TABLE 1 volume percentage of n-butane and n-butane recovery rate in tail gas from butane production and absorption of maleic anhydride by butane method in examples 1 to 6 of the present invention
As can be seen from Table 1, in the embodiments 1 to 6 of the present invention, the recovery rates of n-butane and n-butane in the tail gas from the n-alkane process for preparing maleic anhydride are all high, and the recovery rate of n-butane can reach as high as 99%, which is far superior to the recovery effect of the partial tail gas circulation process technology of CONSER company in the prior art, and the original production process of maleic anhydride is not affected, which indicates that the method of the present invention has an excellent recovery effect on n-butane in the tail gas from the n-alkane process for preparing maleic anhydride, and meanwhile, the method also has the characteristics of simple process, less equipment investment, continuous absorption and desorption of n-butane, stable operation, and very good application prospects.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (7)
1. A method for recovering n-butane in tail gas generated in a butane process for preparing maleic anhydride is characterized by comprising the following steps:
step one, pressurizing the tail gas of the butane method maleic anhydride by using a gas booster (5) and sending the tail gas into a spray washer (4) for water washing and spraying;
step two, sending the tail gas of the butane-process maleic anhydride sprayed by water washing in the step one into an adsorber (1) through a first gas inlet (1-3) and selectively adsorbing the tail gas with an adsorbent entering the adsorber (1) through a first feed inlet (1-1) to obtain an adsorbent adsorbing n-butane and adsorption tail gas, and then discharging the adsorption tail gas through a first gas outlet (1-2) and then burning the tail gas in an incinerator for removal; the adsorbent flows from top to bottom in the adsorber (1) in a plug flow state, and the flow direction of the adsorbent is opposite to the movement and discharge direction of adsorbed tail gas;
step three, the adsorbent for adsorbing the n-butane obtained in the step two enters a screw propeller (2) through a first discharge hole (1-4), then enters a regenerator (3) through a second feed hole (3-1) downwards, is regenerated under the action of water vapor entering the regenerator (3) through a second gas inlet (3-3) to obtain n-butane-rich gas and a regenerated adsorbent, and then the regenerated adsorbent is sent into a riser (6) through a second discharge hole (3-4); the adsorbent for adsorbing the n-butane flows from top to bottom in the regenerator (3) in a plug flow state, and the flow direction of the adsorbent for adsorbing the n-butane is opposite to the flow direction of the movement of the water vapor;
step four, discharging the n-butane-rich gas obtained in the step three through a second gas outlet (3-2), then sending the gas into a condensation tank (7) for cooling and separation to obtain n-butane and water, sending the n-butane into a n-butane tank (8) for storage, and sending the water into a water tank (9) for storage;
and step five, feeding the regenerated adsorbent obtained in the step three into an adsorber (1) through a first feed port (1-1), and then continuously performing the selective adsorption process in the step two, the regeneration process in the step three and the cooling separation process in the step four to continuously recover n-butane in the tail gas of the maleic anhydride preparation by the butane method.
2. The method for recovering n-butane from the tail gas generated in the preparation of maleic anhydride by a butane process according to claim 1, wherein the tail gas generated in the preparation of maleic anhydride by a butane process in the first step comprises the following gas components in percentage by volume: 0.1-0.5% of n-butane, 0.5-2.0% of carbon monoxide, 0.5-2.0% of carbon dioxide, 8-20% of oxygen and the balance of nitrogen.
3. The method for recovering the n-butane in the tail gas generated in the preparation of the maleic anhydride by the butane method according to claim 1, wherein the pressure after the pressurization in the first step is 100kPa to 500 kPa.
4. The method for recovering the n-butane in the tail gas of the butane process for preparing the maleic anhydride according to claim 1, wherein the water temperature for the water washing spray in the first step is 10-50 ℃.
5. The method for recovering n-butane from the tail gas generated in the preparation of maleic anhydride by a butane process according to claim 1, wherein the adsorbent in the second step is a molecular sieve, a modified molecular sieve or a resin adsorbent, and the adsorbent is a spherical adsorbent.
6. The method for recovering the n-butane in the tail gas generated in the preparation of the maleic anhydride by the butane method according to claim 1, wherein the pressure of the water vapor in the third step is 110kPa to 510 kPa.
7. The method for recovering the n-butane in the tail gas generated in the preparation of maleic anhydride by a butane process according to claim 1, wherein the temperature of the condensation tank (7) in the fourth step is 10-40 ℃.
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