CN111499495B - Method for separating and recovering non-acidic oxygen-containing organic matters from Fischer-Tropsch synthesis water - Google Patents
Method for separating and recovering non-acidic oxygen-containing organic matters from Fischer-Tropsch synthesis water Download PDFInfo
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Abstract
The invention relates to a method for separating and recovering non-acidic oxygen-containing organic matters from Fischer-Tropsch synthesis water, which mainly adopts a rectification technology to separate and recover the non-acidic oxygen-containing organic matters from the Fischer-Tropsch synthesis water. The process mainly comprises the following steps: the method comprises the steps of (a) preliminary separation of synthetic water, (b) mixed alcohol separation, (c) ethanol purification, (d) propanol purification, (e) extraction agent recovery, (f) mixed alcohol concentration and (g) mixed alcohol purification. After the Fischer-Tropsch synthesis water is treated by the process, a crude methanol product, an absolute ethanol product, an absolute propanol product and a high-value absolute mixed alcohol product can be obtained. Compared with the prior art, the method has the advantages of simple scheme, large treatment capacity, low energy consumption, high recovery rate, capability of meeting the economic requirement of industrial production and the like, can be widely applied to the treatment of Fischer-Tropsch synthesis water generated in Fischer-Tropsch oil preparation industry, and solves the problems of non-economy and non-environmental protection caused by direct discharge of industrial Fischer-Tropsch synthesis water.
Description
Technical Field
The invention relates to a method for separating and recovering oxygen-containing organic matters from Fischer-Tropsch synthesis water, in particular to a method for separating and recovering non-acidic oxygen-containing organic matters from Fischer-Tropsch synthesis water, which is also an economic and environment-friendly Fischer-Tropsch synthesis water treatment method.
Background
With the great increase of the demand of liquid fuels such as petroleum and the continuous decrease of the available reserve of petroleum resources, the method for producing the liquid fuel in shortage by using raw materials such as coal, natural gas and biomass is more and more highly regarded by people. The most representative indirect liquefaction method of fuels such as coal, natural gas, biomass and the like is a Fischer-Tropsch synthesis method. The method comprises reacting carbon monoxide (CO) and hydrogen (H) produced from coal or other raw materials in the presence of iron-based, cobalt-based or iron-cobalt-based catalyst 2 ) The main synthesis gas is used for catalytically synthesizing hydrocarbon fuel under the conditions of certain temperature and pressure. The indirect liquefaction technology has strong applicability to the quality of raw materials, the quality of produced oil is high, and the variety of products is wide.
Oil preparation process by Fischer-Tropsch synthesis method using carbon monoxide (CO) and hydrogen (H) 2 ) The synthesis gas which is taken as the main raw material generates hydrocarbon oil products under the action of an iron-based, cobalt-based or iron-cobalt-based catalyst, and simultaneously generates oxygen-containing organic matters such as alcohols, aldehydes, ketones, esters, acids and the like and a large amount of water. The water phase generated by the reaction and the main product hydrocarbon oil product can be easily separated, but because oxygen-containing organic matters such as alcohols, organic acids and the like have certain solubility in the water phase, the water phase has one water phaseThe water phase obtained from the quantitative determination of oxygen-containing organic compounds such as alcohols, aldehydes, ketones, esters, acids, etc. is generally called Fischer-Tropsch synthesis water. Because a large amount of synthetic water is generated in the process of producing oil by a Fischer-Tropsch method, millions of tons of synthetic water can be generated due to annual production of millions of tons of oil products, and ten thousand tons of oxygen-containing organic matters can be carried in the synthetic water.
As dozens of oxygen-containing organic matters such as aldehydes, ketones, esters, alcohols, acids and the like are dissolved in Fischer-Tropsch synthesis water (comprising high-temperature Fischer-Tropsch synthesis water, medium-temperature Fischer-Tropsch synthesis water and low-temperature Fischer-Tropsch synthesis water) generated in the oil preparation process by the Fischer-Tropsch synthesis method, the part of the organic matters enables the Fischer-Tropsch synthesis water to be a very complex system, and the system has complex substance types, wide boiling range and low concentration, and has azeotropic and association phenomena among various components, (nearly dozens of oxygen-containing organic matters exist in the synthesis water, the boiling points of the oxygen-containing organic matters are distributed and tightly connected from 20 ℃ to 206 ℃, the total concentration of the oxygen-containing organic matters in the synthesis water is about 1-15 percent, and the azeotropic and association phenomena exist among various substances, so that the problems of high cost, difficulty in meeting the environmental protection requirement, low yield of recovered organic matters and the like are caused by adopting a common organic matter-containing wastewater treatment method and a separation and recovery method of the oxygen-containing organic matters in the water. Therefore, it is necessary to find an economical and effective extraction method for separating and recovering Fischer-Tropsch synthesis water.
Compared with membrane separation and other technologies, the rectification separation technology has the advantages of large treatment capacity, strong applicability and the like. Therefore, aiming at the characteristics that the Fischer-Tropsch synthesis water is complex in substance type and large in treatment capacity, the separation and recovery of the non-acidic oxygen-containing organic matters in the Fischer-Tropsch synthesis water by adopting the rectification method is more reasonable. Regarding the separation and recovery of Fischer-Tropsch synthetic water, chinese patents CN103044217A and CN103373909A propose a treatment method for obtaining basic organic raw materials such as acetaldehyde, propionaldehyde, acetone, ethanol, mixed alcohol and the like finally by carrying out organic acid rectification separation, ketone-alcohol cutting rectification separation, acetaldehyde refining, propionaldehyde acetone rectification separation, acetone refining, propionaldehyde refining, anhydrous fusel separation, alcohol-water separation, aldehyde and ketone hydrogenation reduction, ethanol refining and n-propanol refining on Fischer-Tropsch synthetic water. Although the method adopts the rectification method to orderly separate and recover the non-acidic oxygen-containing organic matters in the Fischer-Tropsch synthesis water, the process has the defects of complicated process and large process energy consumption.
Chinese patents CN101244983A and CN101239886A respectively propose a separation and recovery method of organic matter in low temperature Fischer-Tropsch synthesis reaction water and a separation and recovery method of organic matter in high temperature Fischer-Tropsch synthesis reaction water, the two have the problem that the process is too tedious and the process energy consumption is large, and do not involve the separation and recovery of higher alcohols with more than C3, and the method of quicklime dehydration is introduced in the two processes, so the problem of quicklime recovery and reuse exists, and secondary pollution is possibly caused. Chinese patents CN101492360A and CN101555193A propose a method for applying a dividing wall tower rectification technology to separation and recovery of a Fischer-Tropsch synthesis water phase byproduct, but the dividing wall tower structures proposed by the Chinese patents CN101492360A and CN101555193A have two side sampling streams and have the defect of difficult control in a specific operation process. In addition, the method proposed by the method firstly separates ethanol and propanol and then dehydrates the ethanol and the propanol, so that the number of tower equipment in a separation process is increased, and a quicklime dehydration mode is used, so that the process is more complicated, and the investment in the early stage is more and uneconomical.
Disclosure of Invention
The invention aims to solve the problems of uneconomic efficiency, environmental pollution and the like caused by direct discharge of industrial Fischer-Tropsch synthesis water, and provides a method for separating and recovering non-acidic oxygen-containing organic matters from Fischer-Tropsch synthesis water. The method has the advantages of simple scheme, large treatment capacity, low energy consumption, high recovery rate, capability of meeting the economic requirement of industrial production and the like, and can be widely applied to the treatment of Fischer-Tropsch synthesis water generated in the Fischer-Tropsch process oil production industry.
The object of the invention can be achieved by the following process steps:
a method for separating and recovering non-acidic oxygen-containing organic matters from Fischer-Tropsch synthesis water is characterized by comprising the following steps:
(a) Preliminary segmentation of synthetic water
Taking Fischer-Tropsch synthesis water (1) as a raw material, realizing the segmentation of non-acidic oxygen-containing organic matters in a primary separation tower T1 by utilizing a dividing wall tower rectification technology, adding an inorganic alkali solution at the side of a main tower to prevent organic acids from being extracted at the top and the side line of the main tower, obtaining a crude methanol product (2) mainly comprising methanol, acetaldehyde, acetone, methyl acetate, ethyl acetate and a small amount of ethanol at the top of the tower, extracting at the side line to obtain a mixture (3) mainly comprising ethanol, propanol, butanol, pentanol, hexanol and water, and obtaining an aqueous solution (4) containing a small amount of organic acids and organic acid salts at the bottom of the tower;
(b) Mixed alcohol splitting
Taking a mixture (3) which is extracted from the side line of the step (a) and mainly comprises ethanol, propanol, butanol, pentanol, hexanol and water as a raw material, utilizing a rectification technology to realize the division of mixed alcohol in a mixed alcohol division tower T2, obtaining an azeotropic water solution (5) mainly comprising ethanol, propanol and water at the tower top, obtaining a two-phase solution (6) mainly comprising butanol, pentanol, hexanol and water at the tower bottom, and allowing the two-phase solution (6) at the tower bottom to enter a phase separator A for phase separation to obtain an oil phase material flow (19) mainly comprising the mixed alcohol with more than C3 and a water phase material flow (15) containing a trace of the mixed alcohol with more than C3;
(c) Ethanol purification
Taking the azeotropic water solution (5) obtained at the tower top in the step (b) as a raw material, and adopting an extractive distillation technology to realize dehydration and refining of ethanol in an ethanol refining tower T3, obtaining an absolute ethanol product (7) at the tower top, and obtaining a mixed solution (8) mainly comprising an extracting agent, propanol and water at the tower bottom;
(d) Purification of propanol
Taking the mixed solution (8) obtained at the bottom of the tower in the step (c) as a raw material, further extracting in a propanol extraction tower T4 by adopting an extractive distillation technology to realize partial dehydration of propanol, obtaining a propanol solution (9) with the water content not higher than 6% at the top of the tower, and obtaining a mixed solution (10) mainly containing an extracting agent and water at the bottom of the tower; the method comprises the following steps of (1) taking a propanol solution (9) with the water content not higher than 6% as a raw material, adopting a rectification technology to realize dehydration refining of propanol in a propanol refining tower T5, returning a propanol solution (11) with high water content (about 25%) obtained at the tower top of the propanol refining tower T5 to the middle part of a propanol extraction tower T4, and obtaining an anhydrous propanol product (12) at the tower bottom of the propanol refining tower T5;
(e) Extractant recovery
Taking a mixed solution (10) mainly containing an extracting agent and water as a raw material, and adopting a rectification technology to realize the recycling of the extracting agent in an extracting agent recovery tower T6, so as to obtain high-purity wastewater (13) at the tower top of the extracting agent recovery tower T6 and obtain an extracting agent solution (14) at the tower bottom for recycling;
(f) Mixing, extracting with ethanol, and concentrating
Taking a water phase material flow (15) obtained by phase splitting of a phase splitter A as a raw material, adopting a rectification technology to realize recovery and dehydration treatment of organic matters in a mixed alcohol extraction concentration tower T7, enabling a tower top material flow to enter a phase splitter B for phase splitting, enabling a lower water phase (17) to return to a primary separation tower T1 as a reflux liquid, enabling an upper oil phase material flow (16) and an oil phase material flow (19) obtained by phase splitting of the phase splitter A to enter a mixed alcohol refining tower T8 together, and obtaining high-purity wastewater (18) at the tower bottom of the mixed alcohol extraction concentration tower T7;
(g) Refining of mixed alcohol
The upper oil phase material flow (16) and the oil phase material flow (19) obtained by phase splitting of the phase splitter A are used as raw materials, the rectification technology is adopted to realize mixed alcohol dehydration treatment in a mixed alcohol refining tower T8, the material flow at the top of the tower enters the phase splitter C to carry out phase splitting, the upper oil phase of the phase splitter C is used as a reflux liquid to return to the mixed alcohol refining tower T8, the lower water phase material flow (20) of the phase splitter C returns to the primary phase splitter T1, and a high-value anhydrous mixed alcohol product (21) is obtained at the bottom of the tower.
The Fischer-Tropsch synthesis water (1) contains 1-15% of oxygen-containing organic matters in percentage by mass.
The primary separation tower T1 is a bulkhead rectifying tower, the total number of theoretical plates is 40-120, the number of the theoretical plates of a public rectifying section part (comprising a condenser) positioned at the upper part of the vertical partition plate accounts for 1/7-3/7 of the total number of the theoretical plates, and the number of the theoretical plates of a public stripping section part (comprising a reboiler) positioned at the lower part of the vertical partition plate accounts for 1/7-2/7 of the total number of the theoretical plates; the feeding plate is positioned on the prefractionation side, the theoretical plate number of the position of the feeding plate is 1/6-3/4 (counted from the top of the clapboard to the bottom) of the theoretical plate number of the vertical clapboard, the lateral line extraction port is positioned on the side of the main tower of the clapboard, the theoretical plate number of the lateral line extraction position is 1/4-3/4 (counted from the top of the clapboard to the bottom) of the theoretical plate number of the vertical clapboard, the feeding port of the inorganic alkali solution is positioned from the lateral line extraction port to the bottom of the clapboard, the inorganic alkali is at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium hydroxide, the concentration of the inorganic alkali solution is 1-3 mol/L, the flow rate of the inorganic alkali solution to the raw material flow rate is 0.001-0.005, the reflux ratio is 5-35, the gas phase distribution ratio (prefractionation side to main tower side) is 0.5-20, the liquid phase distribution ratio (prefractionation side to main tower side) is 0.1-2, the tower top temperature is controlled to be 30-80 ℃, and the lateral extraction temperature is controlled to be 50-130 ℃.
The number of theoretical plates of the mixed alcohol dividing tower T2 is 20-60, the feeding position is 1/5-4/5 of the total number of theoretical plates (from the tower top to the tower bottom), the reflux ratio is 2-8, the temperature at the tower top is controlled to be 75-85 ℃, and the temperature at the tower bottom is controlled to be 95-150 ℃; the number of theoretical plates of the T3 of the ethanol refining tower is 25-60, the feeding position is 2/5-4/5 of the total number of theoretical plates (from the top to the bottom), the feeding position of the extractant is 1/6-1/3 of the total number of theoretical plates (from the top to the bottom), the ratio of the extractant to the raw material is 0.5-7, the reflux ratio is 0.2-5, and the temperature at the top of the tower is controlled to be 72-80 ℃; the number of theoretical plates of the propanol extraction tower T4 is 25-60, the feeding position is 3/5-5/6 of the total number of theoretical plates (from the tower top to the tower bottom), the feeding position of the extracting agent is 1/6-2/5 of the total number of theoretical plates (from the tower top to the tower bottom), the ratio of the extracting agent to the raw material is 1-7, the reflux ratio is 0.2-5, and the temperature of the tower top is controlled to be 85-95 ℃; the number of theoretical plates of the propanol refining tower T5 is 15-50, the feeding position is 1/7-4/7 of the total number of theoretical plates (from the tower top to the tower bottom), the reflux ratio is 0.5-5, and the temperature of the tower bottom is controlled to be 90-100 ℃; the number of theoretical plates of the extractant recovery tower T6 is 8-40, the feeding position is 1/4-3/4 of the total number of theoretical plates (from the tower top to the tower bottom), the reflux ratio is 0.1-3, the temperature of the tower bottom is controlled to be 128-180 ℃, and the pressure reduction rectification is carried out.
The number of theoretical plates of the mixed alcohol extracting and concentrating tower T7 is 10-40, the feeding position is 1/4-3/4 of the total number of theoretical plates (from the top to the bottom), a phase separator B is arranged at the top of the tower, the lower layer of water phase in the phase separator flows back into a primary phase separator T1, the upper layer of oil phase material flow (16) and the oil phase material flow (19) from the phase separator A enter a mixed alcohol refining tower T8 together, the reflux ratio is 0.1-3, and the temperature of the bottom of the tower is controlled to be 98-110 ℃.
The number of theoretical plates of the mixed alcohol refining tower T8 is 15-40, the feeding position is 1/15-2/3 of the total number of theoretical plates (from the top to the bottom), a phase separator C is arranged at the top of the tower, an upper oil phase in the phase separator reflows into the tower, a lower water phase reflows into a primary separating tower T1, the reflow ratio is 0.01-3, and the temperature at the bottom of the tower is controlled to be 100-180 ℃.
The extractant used by the ethanol refining tower T3 and the propanol extraction tower T4 is at least one of ethylene glycol, dimethyl sulfoxide, N-methyl pyrrolidone or ethylene glycol with salt, and the same extractant is used by the two towers.
Compared with the prior art, the invention has the beneficial effects that:
the invention has the outstanding advantages that:
the method mainly comprises a continuous system for separating and recovering non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis water, which is composed of eight rectifying towers, and mainly considers the following factors: 1. most of water and organic acid are removed in the first step, most of water in the Fischer-Tropsch synthesis water composition can be removed, and meanwhile, the corrosion of the organic acid to tower equipment is avoided; 2. in the first step of the rectifying process of the dividing wall tower, crude methanol products mainly comprising methanol, acetaldehyde, acetone, methyl acetate, ethyl acetate and a small amount of ethanol are extracted from the tower top, and a mixture mainly comprising ethanol, propanol, butanol, pentanol, hexanol and water is extracted from the side line, so that the characteristics that the content of organic matters such as acetaldehyde, acetone, methyl acetate, ethyl acetate and the like is low, the acetone and the methanol are azeotropic, the methanol and the water are not azeotropic, and other alcohols are azeotropic with the water except the methanol are fully considered; 3. in the second step, the mixed alcohol is divided, an azeotropic water solution mainly comprising ethanol, propanol and water is extracted from the top of the tower, a two-phase solution mainly comprising butanol, pentanol, hexanol and water is extracted from the bottom of the tower, the azeotropic and mutual solubility characteristics of the ethanol and the propanol with water are fully considered, dehydration and refining can be carried out subsequently in an extractive distillation or azeotropic distillation mode, the azeotropic and phase separation characteristics of the higher alcohols such as butanol, pentanol and hexanol with water are fully utilized, and the dehydration and refining of the higher mixed alcohol can be carried out subsequently by the matching of the rectifying tower and the phase separator by fully utilizing the azeotropic and phase separation characteristics of the higher alcohols with water. The whole separation process has reasonable flow, saves the early investment of equipment, saves energy consumption and has good separation effect.
The essential feature of the present invention is that,
1) This application first step utilizes next door tower rectification technique to carry out preliminary segmentation with the ft synthetic water, adopts organic acid in the commodity circulation in order to prevent the top of the tower and side simultaneously, has increased inorganic alkali solution commodity circulation in the main tower side of next door tower to prevent that organic acid from adopting and causing the phenomenon emergence of corruption to follow-up splitter. On the basis, the rectification technology is applied to separating and recovering non-acidic oxygen-containing organic matters from Fischer-Tropsch synthesis water, so that the separation of the anhydrous ethanol, the anhydrous propanol and the anhydrous mixed alcohol is realized, and for example, the ethanol and the propanol are dehydrated and refined by adopting the extractive rectification technology.
2) The invention utilizes the dividing wall column rectification technology in the preliminary segmentation stage of the Fischer-Tropsch synthesis water, greatly reduces the process energy consumption while achieving the separation target, saves one rectification column and related matching equipment, and achieves the design purposes of simplifying the flow, saving the energy consumption and reducing the equipment investment. In order to obtain the anhydrous ethanol and the anhydrous propanol products, the anhydrous ethanol and the anhydrous propanol products with the water contents meeting the national standards are respectively obtained by two-step extractive distillation, and the method is remarkable in that the same extracting agent is used in the two-step extractive distillation in the process flow related to the invention, which means that the mixed solution of the extracting agent and water obtained at the bottom of a tower T4 can be recovered in a single tower, namely a tower T6, if different extracting agents are adopted in two steps, the two towers are required to be respectively recovered in order to obtain a pure circulating extracting agent, the use of the same extracting agent is more reasonable, one extracting agent or entrainer recovery device is reduced, and the corresponding energy consumption is saved. In addition, aiming at the dehydration problem of the mixed alcohol with more than 3 carbon atoms, the invention fully utilizes the azeotropic and phase-splitting characteristics of the mixed alcohol with more than 3 carbon atoms and water, realizes the dehydration purpose of the mixed alcohol with high carbon atoms by the matching use of the rectifying tower and the phase splitter, the whole separation process is similar to the azeotropic distillation process, but avoids the addition of an entrainer, compared with the azeotropic distillation and extraction rectification modes, the process avoids the use of the entrainer or the extractant, avoids the introduction of new impurities and saves energy consumption and a solvent recovery device. In a word, compared with the prior art, the method has the advantages of simple scheme, large treatment capacity, low energy consumption, high recovery rate, capability of meeting the economic requirement of industrial production and the like, and can be widely applied to the treatment of the Fischer-Tropsch synthesis water generated in the Fischer-Tropsch process oil production industry.
3) The method has the advantages that the process is more reasonable and simplified as much as possible in the process design, the simple process means lower equipment and energy investment, only 8 tower equipment and three phase splitters are used in the method, the separation and recovery of non-acidic oxygen-containing organic matters in the Fischer-Tropsch synthesis water are realized, the energy consumption is lower under the same treatment capacity, and dehydrating agents such as quicklime and the like are not required to be added in the process for dehydrating the propanol, so that the additional sewage treatment process is avoided, and the method is economic and energy-saving.
4) The partition tower that adopts in this application adopts the form for the unilateral, has reduced the control degree of difficulty of partition tower in actual industrial operation, realizes stable control more easily.
5) The invention can achieve the purpose of reducing equipment investment and energy consumption on the premise of achieving the separation target by the combined design of reasonable process parameters and structures of each tower device.
Drawings
FIG. 1 is a process flow diagram of the present invention.
In the figure, T1 is a primary separation tower, T2 is a mixed alcohol dividing tower, T3 is an ethanol refining tower, T4 is a propanol extraction tower, T5 is a propanol refining tower, T6 is an extractant recovery tower, T7 is a mixed alcohol concentration tower, and T8 is a mixed alcohol refining tower.
Detailed Description
The invention is further described with reference to the following figures and embodiments.
Example 1
According to the flow shown in figure 1, low-temperature Fischer-Tropsch synthesis water (1) is used as a raw material, the composition of the raw material is shown in a table 1, the raw material enters a primary separation tower T1, the total number of theoretical plates (including a reboiler and a condenser) of the tower is 69, 26 theoretical plates are arranged on the upper side of a vertical clapboard, 11 theoretical plates are arranged on the lower side of the clapboard, the height of the whole clapboard is 32 theoretical plates, a 7 th theoretical plate is counted from the clapboard to the bottom at a feeding position on a pre-fractionation side, a 17 th theoretical plate is counted from the clapboard to the bottom at a side line withdrawing position on a main tower side, a sodium hydroxide solution feeding port is positioned from the side line withdrawing port to the 3 rd theoretical plate at the bottom end of the clapboard, the concentration of the sodium hydroxide solution is 1mol/L, and the ratio of the flow rate of the sodium hydroxide solution to the flow rate of the raw material is 0.0015, the reflux ratio is 25.6, the gas phase distribution ratio (prefractionation side to main tower side) is 4.54, the liquid phase distribution ratio (prefractionation side to main tower side) is 0.72, the tower top temperature is controlled to be 61.60 ℃, the side line extraction temperature is controlled to be 82.94 ℃, a crude methanol product (2) mainly comprising methanol, acetaldehyde, acetone, methyl acetate, ethyl acetate and a small amount of ethanol is obtained at the tower top, the product can be used as fuel or further separated and purified to obtain high-value products comprising methanol, acetaldehyde, acetone and the like, the side line extraction is carried out to obtain a mixture (3) mainly comprising ethanol, propanol, butanol, pentanol, hexanol and water, the mixture enters a mixed alcohol dividing tower T2, and the tower bottom is provided with an aqueous solution (4) containing trace organic acids and organic acid salts; the number of theoretical plates of the mixed alcohol dividing tower T2 is 50, the feeding position is 25 th theoretical plate (from the tower top to the tower bottom), the reflux ratio is 3.5, the temperature at the tower top is controlled to be 79.4 ℃, azeotropic aqueous solution (5) mainly comprising ethanol, propanol and water is obtained at the tower top, and two-phase solution (6) mainly comprising butanol, pentanol, hexanol and water is obtained at the tower bottom;
feeding an azeotropic water solution (5) mainly comprising ethanol, propanol and water into an ethanol refining tower T3, wherein the total number of theoretical plates of the ethanol refining tower T3 is 40, the feeding position is a 22 th theoretical plate (from the top to the bottom of the tower), the feeding position of an extracting agent is a 5 th plate (from the top to the bottom of the tower), ethylene glycol is used as an extracting agent, the ratio of the extracting agent to raw materials is 1.38, the reflux ratio is 3, the temperature at the top of the tower is controlled to be 77.9 ℃, an anhydrous ethanol product (7) is obtained at the top of the tower, and a mixed solution (8) mainly comprising the extracting agent, the propanol and the water is obtained at the bottom of the tower;
feeding a mixed solution (8) mainly containing an extracting agent, propanol and water into a propanol extraction tower T4, wherein the total number of theoretical plates is 40, the feeding position is a 34 th theoretical plate (from the tower top to the tower bottom), the feeding position of the extracting agent is a 4 th plate (from the tower top to the tower bottom), ethylene glycol is used as the extracting agent, the ratio of the extracting agent to raw materials is 4.79, the reflux ratio is 1, the temperature at the tower top is controlled to be 92.1 ℃, a propanol solution (9) with water content not higher than 6% is obtained at the tower top, and a mixed solution (10) mainly containing the extracting agent and water is obtained at the tower bottom;
the method comprises the following steps of (1) enabling a propanol solution (9) with water content not higher than 6% to enter a propanol refining tower T5, enabling the number of total theoretical plates to be 20, enabling the feeding position to be a 3 rd theoretical plate (from the top to the bottom), enabling the reflux ratio to be 1.5, controlling the temperature at the bottom of the tower to be 97.1 ℃, enabling an azeotropic solution (11) of propanol and water obtained at the top of the tower to return to a tower T4, and enabling an anhydrous propanol product (12) to be obtained at the bottom of the tower;
feeding a mixed solution (10) mainly containing an extracting agent and water into an extracting agent recovery tower T6, wherein the total number of theoretical plates is 14, the feeding position is a 7 th theoretical plate (from the top to the bottom of the tower), the reflux ratio is 0.7, the operating pressure is 10kPa, the temperature at the bottom of the tower is controlled to be 132.7 ℃, high-purity wastewater (13) is obtained at the top of the tower, and the extracting agent solution (14) is obtained at the bottom of the tower for recycling; a two-phase solution (6) mainly containing n-butyl alcohol, n-amyl alcohol, n-hexyl alcohol and water enters a phase separator A, a lower layer obtains a water-phase material flow (15) containing trace mixed alcohol with more than 3 carbon atoms, and an upper layer obtains an oil-phase material flow (19) mainly containing the mixed alcohol with more than 3 carbon atoms;
the water phase material flow (15) containing mixed alcohol with trace C3 and above enters a mixed alcohol concentration tower T7, the number of total theoretical plates is 20, the feeding position is the 9 th theoretical plate (from the top to the bottom), the reflux ratio is 0.5, the temperature at the bottom of the tower is controlled to be 100 ℃, the material flow at the top of the tower enters a phase separator B, the lower water phase (17) refluxes into a primary separation tower, the upper oil phase material flow (16) and the material flow (19) enter a mixed alcohol refining tower T8 together, and high-purity wastewater (18) is obtained at the bottom of the tower;
and (3) feeding the material flow (16) and the oil phase material flow (19) obtained by phase separation of the phase separator A into a mixed alcohol refining tower T8 together, wherein the total number of theoretical plates of the mixed alcohol refining tower T8 is 25, the feeding position is the 2 nd theoretical plate (from the top to the bottom), the reflux ratio is 0.01, the temperature at the bottom of the tower is controlled to be 126.5 ℃, the material flow at the top of the tower enters a phase separator C, the upper oil phase of the phase separator C flows back into the mixed alcohol refining tower T8, the lower water phase material flow (20) flows back into a primary separation tower T1, and the high-value anhydrous mixed alcohol product (21) is obtained at the bottom of the tower.
Table 1 process flow stream composition (% by mass)
TABLE 2 results of the separation and recovery of the product
Example 2
According to the flow shown in figure 1, the raw material of high-temperature Fischer-Tropsch synthesis water (1) with the composition shown in Table 3 enters a primary separation tower T1, the total number of theoretical plates of the tower is 60, 25 theoretical plates are arranged on the upper side of a clapboard, 9 theoretical plates are arranged on the lower side of the clapboard, 26 theoretical plates are arranged on the height of the whole clapboard, a feeding position is the 6 th theoretical plate on a pre-fractionation side (counting downwards from the top of the clapboard), a side line extraction position is the 15 th theoretical plate on a main tower side (counting downwards from the top of the clapboard), a sodium hydroxide solution feeding port is arranged from a side line extraction port to the 3 rd theoretical plate at the bottom end of the clapboard, the concentration of a sodium hydroxide solution is 1mol/L, the ratio of the flow rate of the sodium hydroxide solution to the flow rate of the raw material is 0.003, the reflux ratio is 30, the gas phase distribution ratio (the prefractionation side is more than the main tower side) is 1.51, the liquid phase distribution ratio (the prefractionation side is more than the main tower side) is 0.46, the tower top temperature is controlled to be 43.60 ℃, the side line extraction temperature is controlled to be 81.41 ℃, a crude methanol product (2) which mainly comprises methanol, acetaldehyde, acetone, methyl acetate, ethyl acetate and a small amount of ethanol is obtained at the tower top, the product can be used as fuel or further separated and purified to obtain products such as high-value methanol, acetaldehyde, acetone and the like, a mixture (3) which mainly comprises ethanol, propanol, butanol, pentanol, hexanol and water is obtained at the side line extraction and enters a mixed alcohol dividing tower T2, and an aqueous solution (4) containing trace organic acid is obtained at the tower bottom; the number of theoretical plates of the mixed alcohol dividing tower T2 is 45, the feeding position is the 26 th theoretical plate (from the tower top to the tower bottom), the reflux ratio is 3.5, the temperature at the tower top is controlled to be 79.4 ℃, an azeotropic aqueous solution (5) mainly containing ethanol, propanol and water is obtained at the tower top, and a two-phase solution (6) mainly containing butanol, pentanol, hexanol and water is obtained at the tower bottom; feeding an azeotropic water solution (5) mainly containing ethanol, propanol and water into an ethanol refining tower T3, wherein the total number of theoretical plates is 42, the feeding position is 23 th theoretical plate (from the top to the bottom of the tower), the feeding position of an extracting agent is 5 th theoretical plate (from the top to the bottom of the tower), ethylene glycol is used as the extracting agent, the ratio of the extracting agent to raw materials is 1.25, the reflux ratio is 2.8, the temperature at the top of the tower is controlled to be 77.8 ℃, obtaining an anhydrous ethanol product (7) at the top of the tower, and obtaining a mixed solution (8) mainly containing the extracting agent, propanol and water at the bottom of the tower; feeding a mixed solution (8) mainly containing an extracting agent, propanol and water into a propanol extraction tower T4, wherein the total number of theoretical plates is 38, the feeding position is a 32 th theoretical plate (from the tower top to the tower bottom), the feeding position of the extracting agent is a 4 th plate (from the tower top to the tower bottom), ethylene glycol is used as the extracting agent, the ratio of the extracting agent to raw materials is 4.25, the reflux ratio is 1, the temperature at the tower top is controlled to be 92.2 ℃, a propanol solution (9) with water content not higher than 6% is obtained at the tower top, and a mixed solution (10) mainly containing the extracting agent and water is obtained at the tower bottom; the method comprises the following steps of (1) enabling a propanol solution (9) with water content not higher than 6% to enter a propanol refining tower T5, enabling the number of total theoretical plates to be 18, enabling the feeding position to be a 3 rd theoretical plate (from the top to the bottom), enabling the reflux ratio to be 1.5, controlling the temperature at the bottom of the tower to be 97.2 ℃, enabling an azeotropic solution (11) of propanol and water obtained at the top of the tower to return to the tower T4, and enabling an anhydrous propanol product (12) to be obtained at the bottom of the tower; feeding a mixed solution (10) mainly containing an extracting agent and water into an extracting agent recovery tower T6, wherein the total number of theoretical plates is 15, the feeding position is a 7 th theoretical plate (from the top to the bottom of the tower), the reflux ratio is 1.0, the operating pressure is 10kPa, the temperature at the bottom of the tower is controlled to be 132.7 ℃, high-purity wastewater (13) is obtained at the top of the tower, and an extracting agent solution (14) is obtained at the bottom of the tower for recycling; the material flow (6) enters a phase separator A, a water phase material flow (15) containing trace mixed alcohol with more than 3 carbon atoms is obtained at the lower layer, and an oil phase material flow (19) mainly containing the mixed alcohol with more than 3 carbon atoms is obtained at the upper layer; the water phase material flow (15) containing micro mixed alcohol with more than 3 carbon atoms enters a mixed alcohol concentration tower T7, the total theoretical plate number is 22, the feeding position is a 10 th theoretical plate (from the top to the bottom), the reflux ratio is 0.4, the temperature at the bottom of the tower is controlled to be 100 ℃, the material flow at the top of the tower enters a phase splitter B, the lower water phase (17) refluxes into a primary splitter, the upper oil phase material flow (16) and the oil phase material flow (19) obtained by phase splitting of a phase splitter A enter a mixed alcohol refining tower T8 together, and high-purity wastewater (18) is obtained at the bottom of the tower; the upper oil phase material flow (16) and the oil phase material flow (19) obtained by phase separation of the phase separator A enter a mixed alcohol refining tower T8 together, the total number of theoretical plates is 24, the feeding position is the 2 nd theoretical plate (from the top to the bottom), the reflux ratio is 0.05, the temperature at the bottom of the tower is controlled to be 125.0 ℃, the material flow at the top of the tower enters the phase separator C, the upper oil phase flows back into the tower, the lower water phase material flow (20) flows back into the primary separation tower T1, and the high-value anhydrous mixed alcohol product (21) is obtained at the bottom of the tower.
TABLE 3 Process flow stream composition (% by mass)
TABLE 4 results of separation and recovery of product
The method has the advantages that the separation process is reasonably set, the rectification technology is applied to separate and recover the non-acidic oxygen-containing organic matters in the Fischer-Tropsch synthesis water, the Fischer-Tropsch synthesis water generated under different working conditions is fully illustrated by the embodiment, the treatment of the Fischer-Tropsch synthesis water can be effectively realized, crude methanol products, absolute ethyl alcohol, absolute propyl alcohol and anhydrous mixed alcohol products with high value of more than C3 can be obtained in the process, the treated wastewater can be subjected to subsequent organic acid recovery, and can also be recycled to the synthesis gas preparation stage for water supplement of slurry prepared by rolling solid fuels such as coal. Compared with the prior art, the method has the advantages of simple scheme, large treatment capacity, low energy consumption, high recovery rate, capability of meeting the economic requirement of industrial production and the like, and can be widely applied to the treatment of the Fischer-Tropsch synthesis water generated in the Fischer-Tropsch process oil production industry.
The invention is applicable to the prior art where nothing is said.
Claims (7)
1. A method for separating and recovering non-acidic oxygen-containing organic matters from Fischer-Tropsch synthesis water is characterized by comprising the following steps:
(a) Preliminary segmentation of synthetic water
Taking Fischer-Tropsch synthesis water (1) as a raw material, realizing the segmentation of non-acidic oxygen-containing organic matters in a primary separation tower T1 by utilizing a dividing wall tower rectification technology, adding an inorganic alkali solution at the side of a main tower to prevent organic acids from being extracted at the top and the side line of the main tower, obtaining a crude methanol product (2) mainly comprising methanol, acetaldehyde, acetone, methyl acetate, ethyl acetate and a small amount of ethanol at the top of the tower, extracting at the side line to obtain a mixture (3) mainly comprising ethanol, propanol, butanol, pentanol, hexanol and water, and obtaining a wastewater solution (4) containing a small amount of organic acids and organic acid salts at the bottom of the tower;
(b) Mixed alcohol splitting
Taking a mixture (3) which is extracted from the side line of the step (a) and mainly comprises ethanol, propanol, butanol, pentanol, hexanol and water as a raw material, utilizing a rectification technology to realize the division of mixed alcohol in a mixed alcohol division tower T2, obtaining an azeotropic water solution (5) mainly comprising ethanol, propanol and water at the tower top, obtaining a two-phase solution (6) mainly comprising butanol, pentanol, hexanol and water at the tower bottom, and allowing the two-phase solution (6) at the tower bottom to enter a phase separator A for phase separation to obtain an oil phase material flow (19) mainly comprising the mixed alcohol with more than 3 carbon atoms and a water phase material flow (15) containing a trace of the mixed alcohol with more than 3 carbon atoms;
(c) Ethanol purification
Taking the azeotropic water solution (5) obtained at the tower top in the step (b) as a raw material, and adopting an extractive distillation technology to realize dehydration and refining of ethanol in an ethanol refining tower T3, so as to obtain an absolute ethanol product (7) at the tower top and obtain a mixed solution (8) mainly comprising an extracting agent, propanol and water at the tower bottom;
(d) Purification of propanol
Taking the mixed solution (8) obtained at the bottom of the tower in the step (c) as a raw material, further extracting in a propanol extraction tower T4 by adopting an extractive distillation technology to realize partial dehydration of propanol, obtaining a propanol solution (9) with the water content not higher than 6% at the top of the tower, and obtaining a mixed solution (10) mainly containing an extracting agent and water at the bottom of the tower; the method comprises the following steps of (1) taking a propanol solution (9) with the water content not higher than 6% as a raw material, adopting a rectification technology to realize dehydration and refining of propanol in a propanol refining tower T5, returning a propanol solution (11) with high water content obtained at the tower top of the propanol refining tower T5 to the middle part of a propanol extraction tower T4, and obtaining an anhydrous propanol product (12) at the tower bottom of the propanol refining tower T5;
(e) Extractant recovery
Taking a mixed solution (10) mainly containing an extracting agent and water as a raw material, and adopting a rectification technology to realize the recycling of the extracting agent in an extracting agent recovery tower T6, so as to obtain high-purity wastewater (13) at the top of the extracting agent recovery tower T6 and obtain an extracting agent solution (14) at the bottom of the extracting agent recovery tower for recycling;
(f) Mixing, extracting with ethanol, and concentrating
Taking a water phase material flow (15) obtained by phase splitting of a phase splitter A as a raw material, adopting a rectification technology to realize recovery and dehydration treatment of organic matters in a mixed alcohol extraction concentration tower T7, enabling a tower top material flow to enter a phase splitter B for phase splitting, enabling a lower water phase (17) to return to a primary separation tower T1 as a reflux liquid, enabling an upper oil phase material flow (16) and an oil phase material flow (19) obtained by phase splitting of the phase splitter A to enter a mixed alcohol refining tower T8 together, and obtaining high-purity wastewater (18) at the tower bottom of the mixed alcohol extraction concentration tower T7;
(g) Refining of mixed alcohols
Taking an upper oil phase material flow (16) of a phase separator B and an oil phase material flow (19) obtained by phase separation of a phase separator A as raw materials, adopting a rectification technology to realize mixed alcohol dehydration treatment in a mixed alcohol refining tower T8, enabling a tower top material flow to enter a phase separator C for phase separation, enabling an upper oil phase of the phase separator C to return to the mixed alcohol refining tower T8 as a reflux liquid, enabling a lower water phase material flow (20) of the phase separator C to return to a primary separation tower T1, and obtaining a high-value anhydrous mixed alcohol product (21) at the tower bottom.
2. The method for separating and recovering non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis water according to claim 1, wherein the Fischer-Tropsch synthesis water raw material (1) contains 1-15% of oxygen-containing organic matters by mass percent.
3. The method for separating and recovering non-acidic oxygen-containing organic matters from Fischer-Tropsch synthesis water as claimed in claim 1, wherein the preliminary separation tower T1 is a bulkhead rectifying tower, the total number of theoretical plates is 40-120, the theoretical plates of the common rectifying section part (including a condenser) positioned at the upper part of the vertical partition plate account for 1/7-3/7 of the total number of theoretical plates, and the theoretical plates of the common stripping section part (including a reboiler) positioned at the lower part of the vertical partition plate account for 1/7-2/7 of the total number of theoretical plates; the device comprises a baffle, a pre-fractionating side, a side line extraction outlet, an inorganic alkali feed inlet, a gas phase distribution ratio (the pre-fractionating side is higher than the main tower side) and a liquid phase distribution ratio (the pre-fractionating side is higher than the main tower side) and is 0.1-2, the tower top temperature is controlled to be 30-80 ℃, the side line extraction temperature is controlled to be 50-130 ℃.
4. The method for separating and recovering non-acidic oxygen-containing organic matters from Fischer-Tropsch synthesis water according to claim 1, wherein the theoretical plate number of the mixed alcohol dividing tower T2 is 20-60, the feeding position is 1/5-4/5 of the total theoretical plate number (from the tower top to the tower bottom), the reflux ratio is 2-8, the temperature at the tower top is controlled to be 75-85 ℃, and the temperature at the tower bottom is controlled to be 95-150 ℃; the number of theoretical plates of the T3 of the ethanol refining tower is 25-60, the feeding position is 2/5-4/5 of the total number of theoretical plates (from the top to the bottom), the feeding position of the extractant is 1/6-1/3 of the total number of theoretical plates (from the top to the bottom), the ratio of the extractant to the raw material is 0.5-7, the reflux ratio is 0.2-5, and the temperature at the top of the tower is controlled to be 72-80 ℃;
the number of theoretical plates of the propanol extraction tower T4 is 25-60, the feeding position is 3/5-5/6 of the total number of theoretical plates (from the tower top to the tower bottom), the feeding position of the extractant is 1/6-2/5 of the total number of theoretical plates (from the tower top to the tower bottom), the ratio of the extractant to the raw material is 1-7, the reflux ratio is 0.2-5, and the temperature of the tower top is controlled to be 85-95 ℃;
the number of theoretical plates of the propanol refining tower T5 is 15-50, the feeding position is 1/7-4/7 of the total number of theoretical plates (from the tower top to the tower bottom), the reflux ratio is 0.5-5, and the temperature of the tower bottom is controlled to be 90-100 ℃;
the number of theoretical plates of the extractant recovery tower T6 is 8-40, the feeding position is 1/4-3/4 of the total number of theoretical plates (from the tower top to the tower bottom), the reflux ratio is 0.1-3, the temperature of the tower bottom is controlled to be 128-180 ℃, and the pressure reduction rectification is carried out.
5. The method for separating and recovering non-acidic oxygen-containing organic matters from Fischer-Tropsch synthesis water as claimed in claim 1, wherein the number of theoretical plates of the mixed alcohol concentrating tower T7 is 10-40, the feeding position is 1/4-3/4 of the total number of theoretical plates (from the top to the bottom), the top of the tower is provided with a phase separator B, the lower water phase in the phase separator B flows back into the primary separation tower T1, the upper oil phase stream (16) of the phase separator B and the oil phase stream (19) from the phase separator A enter the mixed alcohol refining tower T8 together, the reflux ratio is 0.1-3, and the temperature of the bottom of the tower is controlled to be 98-110 ℃.
6. The method for separating and recovering non-acidic oxygen-containing organic matters from Fischer-Tropsch synthesis water according to claim 1, wherein the number of theoretical plates of the mixed alcohol refining tower T8 is 15-40, the feeding position is 1/15-2/3 of the total number of the theoretical plates (from the top to the bottom), the top of the tower is provided with a phase separator C, the lower layer of the phase separator C is refluxed into the primary separation tower T1, the reflux ratio is 0.01-3, and the bottom temperature is controlled to be 100-180 ℃.
7. The method for separating and recovering non-acidic oxygen-containing organic matters from Fischer-Tropsch synthesis water according to claim 1, wherein the extractant used in the ethanol refining tower T3 and the propanol extraction tower T4 is at least one of ethylene glycol, dimethyl sulfoxide, N-methyl pyrrolidone or ethylene glycol with salt, and the same extractant is used in both towers.
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