CN111573761A - Method and system for separating and recovering non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis water - Google Patents

Method and system for separating and recovering non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis water Download PDF

Info

Publication number
CN111573761A
CN111573761A CN202010329252.4A CN202010329252A CN111573761A CN 111573761 A CN111573761 A CN 111573761A CN 202010329252 A CN202010329252 A CN 202010329252A CN 111573761 A CN111573761 A CN 111573761A
Authority
CN
China
Prior art keywords
phase
propanol
solution
water
tower
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010329252.4A
Other languages
Chinese (zh)
Inventor
郭中山
李春利
赵建宁
李�浩
方静
李虎
王峰
杨占奇
沈永斌
杨靖华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hebei University of Technology
National Energy Group Ningxia Coal Industry Co Ltd
Original Assignee
Hebei University of Technology
National Energy Group Ningxia Coal Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hebei University of Technology, National Energy Group Ningxia Coal Industry Co Ltd filed Critical Hebei University of Technology
Priority to CN202010329252.4A priority Critical patent/CN111573761A/en
Publication of CN111573761A publication Critical patent/CN111573761A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to the technical field of separation and recovery of Fischer-Tropsch synthesis water, in particular to a method and a system for separating and recovering non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis water, wherein the method comprises the following steps: (a) concentrating the Fischer-Tropsch synthesis water by using a non-acidic oxygen-containing organic substance to obtain organic acid-containing wastewater and a non-acidic oxygen-containing organic substance aqueous solution; (b) cutting the non-acidic oxygen-containing organic matter aqueous solution to obtain a crude methanol product, a two-phase solution and a mixed solution I; then, carrying out phase separation on the two-phase solution to obtain a water phase material flow and an oil phase material flow; (c) refining and separating the mixed solution I to obtain an absolute ethyl alcohol product, an absolute propyl alcohol product and wastewater I; (d) and carrying out alcohol mixing concentration and alcohol mixing refining on the water phase material flow and the oil phase material flow to obtain an anhydrous alcohol mixing product and wastewater II. The method of the invention adopts the specific steps, so that the whole separation and recovery process is simplified, and the method has the advantage of high recovery rate.

Description

Method and system for separating and recovering non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis water
Technical Field
The invention relates to the technical field of separation and recovery of Fischer-Tropsch synthesis water, in particular to a method and a system for separating and recovering non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis water.
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 fuels which are in short supply from raw materials such as coal, natural gas, biomass and the like is more and more highly valued by people.
The most representative of indirect liquefaction methods for fuels such as coal, natural gas, and biomass is the 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 catalyst2) Synthesis gas of main partThe process for catalytically synthesizing hydrocarbon fuel under the condition 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 products are various.
The Fischer-Tropsch synthesis process for preparing oil specifically uses 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. In the oil production process, the water phase generated by the reaction and the main product hydrocarbon oil product generated can be separated very simply, 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 certain amount of oxygen-containing organic matters such as alcohols, aldehydes, ketones, esters, acids and the like, and the obtained water phase 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 by 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 can be 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 become a very complex system, because the substance in the system is complex in type, wide in boiling range, low in concentration (nearly dozens of oxygen-containing organic substances exist in synthetic water, the boiling points of the oxygen-containing organic substances are distributed and tightly connected from 20 ℃ to 206 ℃, the total concentration of the oxygen-containing organic substances in the synthetic water is about 1% -15%), and azeotropic and association phenomena exist among various substances, therefore, the method adopts a common method for treating waste water containing organic matters and a method for separating and recovering the oxygen-containing organic matters in the water to treat the industrial Fischer-Tropsch synthesis water, and has the problems of high cost, difficult environmental protection, low yield of recovered organic products and the like. Therefore, it is necessary to find an economical and effective extraction method for separating and recovering Fischer-Tropsch synthesis water.
At present, compared with technologies such as membrane separation, the separation technology of the rectification method 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.
CN103044217A discloses a method for treating non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis reaction water, which comprises the following steps: the Fischer-Tropsch synthesis reaction water is subjected to (a) organic acid rectification separation, (b) ketone alcohol cutting rectification separation, (c) acetaldehyde refining, (d) propionaldehyde acetone rectification separation, (e) acetone refining, (f) propionaldehyde refining, (g) anhydrous fusel separation, (h) alcohol water separation, (i) aldehyde and ketone hydrogenation reduction, (j) ethanol refining and (k) n-propanol refining, and finally basic organic raw materials such as acetaldehyde, propionaldehyde, acetone, ethanol, n-propanol, mixed alcohol and the like are obtained.
CN103373909A discloses a method for separating and recovering non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis reaction water, which comprises the following steps: the Fischer-Tropsch synthesis reaction water is subjected to 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 to finally obtain basic organic raw materials such as acetaldehyde, propionaldehyde, acetone, ethanol, n-propanol, mixed alcohol and the like.
Although the rectification method is adopted to orderly separate and recover the non-acidic oxygen-containing organic matters in the Fischer-Tropsch synthesis water, the processes in the two patent applications have the defects of complicated process and high process energy consumption.
CN101244983A discloses a method for separating and recovering organic matters in low-temperature Fischer-Tropsch synthesis reaction water, which comprises the following parts: (1) rectifying and separating methanol/ethanol after the organic acid is rectified and removed; (2) extracting, rectifying and separating methanol/ketone; (3) separating and recovering acetone-butanone; (4) refining acetone; (5) removing water from butanone aqueous solution to obtain butanone product; (6) recovering and separating the n-propanol; further rectifying the alcohol-containing aqueous solution obtained at the bottom of the methanol/ethanol rectifying tower, obtaining ethanol containing a small amount of water at the tower top, obtaining an aqueous solution containing n-propanol at the tower bottom, concentrating and rectifying the aqueous solution containing n-propanol in an n-propanol concentration tower, adding quicklime, and distilling to obtain an n-propanol product; (7) absolute ethyl alcohol is prepared by a constant boiling rectification method.
CN101239886A discloses a method for separating and recovering organic matters in high-temperature Fischer-Tropsch synthesis reaction water, which comprises the following process steps: (1) separating and recovering acetaldehyde after the organic acid is removed by rectification; (2) rectifying and separating ketone/n-propanol; (3) rectifying and separating acetone/butanone (4) refining acetone; (5) butanone/ethanol extraction separation; (6) rectifying and separating ethanol/n-propanol; further rectifying the alcohol-containing aqueous solution obtained at the bottom of the ketone/n-propanol separation and rectification tower to obtain ethanol containing a small amount of water at the tower top, obtaining an aqueous solution (7) containing n-propanol at the tower bottom, and performing azeotropic rectification on the ethanol solution obtained by extraction and separation and the ethanol solution from which the n-propanol is separated to prepare anhydrous ethanol; (8) adding quicklime into the water solution of the n-propanol, distilling to obtain an n-propanol product
The two patent applications also have the problems of complicated process and high energy consumption of the process, and the two processes introduce a quicklime dehydration method, so that the problems of quicklime recycling and possible secondary pollution exist.
CN101492360A discloses a method for separating aqueous phase byproduct of fischer-tropsch synthesis, comprising the following steps: the water phase by-product enters the middle part of a common rectifying tower 1, a distillate stream I with a boiling range of 50-120 ℃ is extracted at the lateral line, a light component with a boiling point of less than 40 ℃ is obtained at the top of the tower, and a heavy component with a boiling point of more than 120 ℃ is obtained at the bottom of the tower; the technical scheme that the basic organic raw materials of acetone, methanol, ethanol, n-propanol and acetic acid are obtained after the side line distillate is rectified and separated by the separation tower 2, the extractive distillation tower 3, the azeotropic distillation tower 4, the acetic acid extraction tower 5, the solvent recovery tower 6 and the extractant recovery tower 7 better solves the problem, and can be applied to the industrial production for treating the aqueous phase byproduct of the Fischer-Tropsch synthesis.
CN101555193A discloses a separation method of a Fischer-Tropsch synthesis water phase byproduct, which comprises the following steps: the water phase by-product enters the middle part of a common rectifying tower 1, a distillate stream I with a boiling range of 50-120 ℃ is extracted at the lateral line, a light component with a boiling point of less than 40 ℃ is obtained at the top of the tower, and a heavy component with a boiling point of more than 120 ℃ is obtained at the bottom of the tower; the technical scheme that the side line distillate is rectified and separated by the separation tower 2, the azeotropic rectifying tower 3, the acetic acid extraction tower 4 and the extractant recovery tower 5 to obtain the methanol and acetone solution, ethanol, n-propanol and acetic acid basic organic raw materials better solves the problem, and can be applied to industrial production for treating the aqueous phase byproduct of Fischer-Tropsch synthesis.
Both of these patent applications propose a method of applying the dividing wall column rectification technology to the separation and recovery of the aqueous phase byproduct of the Fischer-Tropsch synthesis, but the dividing wall column structure proposed by the two patent applications has two side sampling streams and has the defect of difficult control in the specific operation process. In addition, the proposed method separates ethanol and propanol and then dehydrates them, which makes the process complicated and uneconomical.
Disclosure of Invention
The invention aims to overcome the defects of complicated separation and recovery process and low recovery rate in the prior art, and provides a method and a system for separating and recovering non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis water, wherein the method has the advantages of simple steps and high recovery rate, and can obtain specific products, particularly high-purity crude methanol products, anhydrous ethanol products, anhydrous propanol products, anhydrous alcohol-mixed products and wastewater products, and the purity is even up to 99.999 wt%.
In order to achieve the above object, the first aspect of the present invention provides a method for separating and recovering non-acidic oxygen-containing organic substances in fischer-tropsch synthesis water, which comprises the following steps:
(a) concentrating the Fischer-Tropsch synthesis water by using a non-acidic oxygen-containing organic substance to obtain organic acid-containing wastewater and a non-acidic oxygen-containing organic substance aqueous solution;
(b) cutting the non-acidic oxygen-containing organic matter aqueous solution to obtain a crude methanol product, a two-phase solution and a mixed solution I; then, carrying out phase separation on the two-phase solution to obtain a water phase material flow and an oil phase material flow;
(c) refining and separating the mixed solution I to obtain an absolute ethyl alcohol product, an absolute propyl alcohol product and wastewater I;
(d) and carrying out alcohol mixing concentration and alcohol mixing refining on the water phase material flow and the oil phase material flow to obtain an anhydrous alcohol mixing product and wastewater II.
The invention provides a separation and recovery system of non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis water, which comprises a first rectifying tower and a bulkhead rectifying tower; the bulkhead rectifying tower is provided with a lateral line extraction unit, and the lateral line extraction unit is externally connected with a rectifying mechanism I; a discharge hole at the bottom of the bulkhead rectifying tower is communicated with a first phase separator through a pipeline, and the first phase separator is communicated with a rectifying mechanism II;
the first rectifying tower is used for concentrating non-acidic oxygen-containing organic matters in the Fischer-Tropsch synthesis water to obtain organic acid-containing wastewater and a non-acidic oxygen-containing organic matter aqueous solution;
the side-draw unit is used for side-draw to obtain a mixed solution I;
the rectification mechanism I is used for respectively refining and separating ethanol and propanol from the mixed solution I;
and the rectifying mechanism II is used for concentrating and refining the mixed alcohol obtained by phase separation of the first phase separator.
Compared with the prior art, the method for separating and recovering non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis water has the advantages that the whole separation and recovery process is simplified, the method has the advantage of high recovery rate, specific products can be obtained, specifically a high-purity crude methanol product, an anhydrous ethanol product, an anhydrous propanol product, an anhydrous alcohol-mixing product and a wastewater product, the purity is even up to 99.999 wt%, and the purity of the obtained wastewater product is more than 97.7 wt%.
The separation and recovery system provided by the invention adopts a system comprising a first rectifying tower and a bulkhead rectifying tower, the bulkhead rectifying tower is provided with a lateral line extraction unit, and the lateral line extraction unit is externally connected with a rectifying mechanism I; a discharge hole at the bottom of the bulkhead rectifying tower is communicated with a first phase separator through a pipeline, and the first phase separator is communicated with a rectifying mechanism II; compared with the prior art, on one hand, the aim of dehydration and refining of mixed alcohol can be fulfilled and the use of an entrainer or an extractant can be avoided due to the fact that the bulkhead rectifying tower and the rectifying mechanism II are matched with the phase separator, so that the introduction of new impurities is avoided, and energy consumption and a solvent recovery device are saved; on the other hand, the method is simplified and easy to control, and can obtain high recovery rate.
Compared with the prior art, the method has the advantages of simple separation method, high recovery rate, large treatment capacity, low energy consumption and capability of meeting the economic requirement of industrial production, and can be widely applied to the treatment of Fischer-Tropsch synthesis water generated in the Fischer-Tropsch process oil production industry.
Drawings
FIG. 1 is a schematic view of the structure of the separation and recovery system of the present invention.
Description of the reference numerals
1-Fischer-Tropsch synthesis water 2-non-acidic oxygen-containing organic matter aqueous solution 3-organic acid-containing wastewater
4-crude methanol product 5-Mixed solution I6-two-phase solution
7-extractant I8-absolute ethyl alcohol product 9-mixed solution II
10-extractant II 11-propanol solution I12-mixed solution III
13-propanol solution II 14-Anhydrous propanol product 15-wastewater I
16-extractant solution 17-aqueous phase stream 18-upper oil phase I
19-wastewater II 20-oil phase material flow 21-lower layer water phase II
22-anhydrous alcohol-mixed product T1-first rectifying tower T2-bulkhead rectifying tower
T3-third rectifying tower T4-fourth rectifying tower T5-fifth rectifying tower
T6-sixth rectifying tower T7-seventh rectifying tower T8-eighth rectifying tower
T9-first phase splitter T10-second phase splitter T11-third phase splitter
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for separating and recovering non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis water, which comprises the following steps:
(a) concentrating the Fischer-Tropsch synthesis water by using a non-acidic oxygen-containing organic substance to obtain organic acid-containing wastewater and a non-acidic oxygen-containing organic substance aqueous solution;
(b) cutting the non-acidic oxygen-containing organic matter aqueous solution to obtain a crude methanol product, a two-phase solution and a mixed solution I; then, carrying out phase separation on the two-phase solution to obtain a water phase material flow and an oil phase material flow;
(c) refining and separating the mixed solution I to obtain an absolute ethyl alcohol product, an absolute propyl alcohol product and wastewater I;
(d) and carrying out alcohol mixing concentration and alcohol mixing refining on the water phase material flow and the oil phase material flow to obtain an anhydrous alcohol mixing product and wastewater II.
In the present invention, the organic acid-containing wastewater contains a trace amount of organic acid, and the concentration of the organic acid is not limited in the present invention, and the lower the concentration, the better the concentration.
The present invention is not limited to the method for concentrating the non-acidic oxygen-containing organic substance in the step (a), the method for dividing the oxygen-containing organic substance in the step (b), the method for purifying and separating the oxygen-containing organic substance in the step (c), and the method for concentrating and purifying the mixed alcohol in the step (d), as long as the above-mentioned respective products can be obtained. Preferably, the concentration of the non-acidic oxygen-containing organic matter in the step (a), the refining separation in the step (c) and the concentration and refining of the mixed alcohol in the step (d) are respectively carried out by adopting a rectification method, and the division in the step (b) is carried out by adopting a dividing wall column rectification method; in this preferred case, in the present invention, the reflux ratio is a reflux ratio of each corresponding column in a conventional definition well known in the art.
The invention has no restriction on the concentration process of the non-acidic oxygen-containing organic matters in the step (a), as long as the non-acidic oxygen-containing organic matters can be separated from the Fischer-Tropsch synthesis water as much as possible; preferably, the conditions for the concentration of the non-acidic oxygen-containing organic substance in step (a) comprise: the concentration temperature of the non-acidic oxygen-containing organic matter is 65-90 ℃. The concentration temperature of the non-acidic oxygen-containing organic matters is controlled to be 65-90 ℃ so as to obtain non-acidic oxygen-containing organic matter aqueous solution and organic acid-containing wastewater. The concentration temperature of the non-acidic oxygen-containing organic matter is the tower top temperature of the first rectifying tower.
Preferably, the conditions for concentrating the non-acidic oxygen-containing organic substance in step (a) further comprise: the reflux ratio is 2-8. According to the preferred embodiment of the invention, the specific high-concentration product can be obtained, and the separation and recovery rate of the non-acidic oxygen-containing organic matter can be improved.
The invention has no limitation on the non-acidic oxygen-containing organic matter aqueous solution as long as the subsequent non-acidic oxygen-containing organic matter can be better separated. Preferably, the water content of the non-acidic oxygen-containing organic matter aqueous solution is 25-35 wt%. Preferably, the non-acidic oxygen-containing organic substance aqueous solution contains at least one of aldehydes, ketones, esters, and alcohol compounds.
In a preferred embodiment of the present invention, the dividing in step (b) comprises two stages of temperature control: the first stage temperature is 40-75 deg.C, and the second stage temperature is 75-85 deg.C. In the two-stage temperature control, the temperature of the first stage is controlled to be 40-75 ℃ to obtain a crude methanol product, and the temperature of the second stage is controlled to be 75-85 ℃ to obtain a mixed solution I and obtain a two-phase solution at the same time. For example, when the partition in step (b) is performed by a dividing wall distillation method, the temperature of the top of the dividing wall distillation column (i.e., the first-stage temperature) is controlled to be 40 to 75 ℃ to obtain a crude methanol product, the temperature of the side draw of the dividing wall distillation column (i.e., the second-stage temperature) is controlled to be 75 to 85 ℃ to obtain a mixed solution I, and a two-phase solution is obtained at the bottom of the column.
The present invention specifically limits the conditions of the splitting described in step (b) to obtain the specific high purity product of the present invention; preferably, the conditions for the segmentation in step (b) include: the reflux ratio is 8-20.
Preferably, the conditions for the segmentation in step (b) further comprise: the vapor phase distribution ratio in the process of cutting the non-acidic oxygen-containing organic matter water solution is 0.5-3, and the liquid phase distribution ratio is 0.5-2.5.
According to a preferred embodiment of the present invention, the step (b) comprises: and (2) cutting the non-acidic oxygen-containing organic matter aqueous solution, wherein the cutting process comprises two sections of temperature control: controlling the temperature of the first section at 40-75 ℃ to obtain a crude methanol product, and controlling the temperature of the second section at 75-85 ℃ to obtain a mixed solution I and obtain a two-phase solution simultaneously, wherein the dividing conditions comprise: the vapor phase distribution ratio is 0.5-3, the liquid phase distribution ratio is 0.5-2.5, and the reflux ratio is 8-20; and then carrying out phase separation on the two-phase solution to obtain a water phase material flow and an oil phase material flow.
In the present invention, the vapor phase distribution ratio and the liquid phase distribution ratio are conventional explanations in the art and are well known to those skilled in the art; for example, when the present invention preferably employs a dividing wall column rectification technique to perform the division, the vapor distribution ratio refers to the ratio of the prefractionation side to the main column side in a conventionally explained dividing wall column, and the liquid distribution ratio refers to the ratio of the prefractionation side to the main column side in a conventionally explained dividing wall column.
The present invention is not limited to the composition of the crude methanol product, as long as the specific product of the present invention is obtained and the recovery rate of the non-acidic oxygen-containing organic substance is improved. For better separation of non-acidic oxygenated organics, the crude methanol product contains at least one of acetaldehyde, acetone, methyl acetate, ethyl acetate, and ethanol, and methanol; preferably, the crude methanol product contains acetaldehyde, acetone, methyl acetate, ethyl acetate, ethanol and methanol, and the crude methanol product is dominated by acetaldehyde, acetone, methyl acetate, ethyl acetate and methanol and contains a small amount of ethanol. The crude methanol product can be directly used as fuel, or further separated and purified to obtain high-value products such as methanol, acetaldehyde and acetone.
In the present invention, the two-phase solution refers to a mixed solution of an aqueous phase and an oil phase. In order to fully utilize the phase separation to separate the mixed alcohol, the two-phase solution contains at least one of butanol, pentanol and hexanol and water; preferably, the two-phase solution contains butanol, pentanol, hexanol and water. The preferred scheme of the invention is more beneficial to the separation of more mixed alcohol above C3 by phase separation.
The Fischer-Tropsch synthesis water to be treated is not limited, and can be low-temperature Fischer-Tropsch synthesis water or high-temperature Fischer-Tropsch synthesis water. Preferably, the Fischer-Tropsch synthesis water contains 1 to 15 wt% of oxygenated organics.
According to a preferred embodiment of the present invention, the refining separation of step (c) comprises the following processes:
(c-1) contacting the mixed solution I with an extracting agent I to perform ethanol extraction rectification to obtain an absolute ethanol product and a mixed solution II;
(c-2) contacting the mixed solution II with an extracting agent II to perform propanol extraction and rectification to obtain a water-containing propanol solution I and a mixed solution III;
(c-3) dehydrating and refining the propanol solution I to obtain the anhydrous propanol product and a water-containing propanol solution II; optionally refluxing the propanol solution II to the step (c-2) and adding the propanol solution II into the mixed solution II;
and (c-4) carrying out reduced pressure rectification on the mixed solution III to recover the extracting agent, so as to obtain the wastewater I and the extracting agent solution.
According to the invention, by adopting the preferable scheme of the step (c), the anhydrous ethanol product and the anhydrous propanol product with the water contents meeting the national standard are respectively obtained, wherein the water content in the anhydrous ethanol product is less than 5 wt%, and the water content in the anhydrous propanol product is less than 5 wt%.
The method has no limitation on the condition of ethanol extraction and rectification in the step (c-1), as long as an absolute ethanol product and a mixed solution II can be obtained, and the absolute ethanol can be better separated; preferably, the ethanol extractive distillation conditions in step (c-1) include: the extraction temperature of the ethanol is 72-80 ℃. The ethanol extraction temperature refers to the tower top temperature of a third rectifying tower.
In order to separate the anhydrous ethanol better, the ethanol extractive distillation conditions in the step (c-1) further comprise: the reflux ratio is 0.2-5.
Preferably, in the step (c-1), the mass ratio of the extractant I to the mixed solution I is 0.5 to 7.
The invention has no restriction on the condition of the extraction and rectification of the propanol in the step (c-2), as long as aqueous propanol solution I and mixed solution III can be obtained, and the better separation of the propanol is facilitated; preferably, the conditions for the extractive distillation of propanol in step (c-2) include: the temperature of the propanol extraction is 85-95 ℃. The propanol extraction temperature refers to the tower top temperature of the fourth rectifying tower.
For better separation of propanol, the conditions for extractive distillation of propanol in step (c-2) further comprise: the reflux ratio is 0.2-5.
Preferably, in the step (c-2), the mass ratio of the extracting agent II to the mixed solution II is 1-7.
The invention has no restriction on the condition of the dehydration and refining of the propanol in the step (c-3), as long as an anhydrous propanol product and a hydrous propanol solution II can be obtained, and the anhydrous propanol can be better separated; preferably, the conditions for dehydrating and refining propanol in the step (c-3) include: the dehydration temperature of the propanol is 90-100 ℃. The dehydration temperature of propanol means the bottom temperature of the fifth rectifying column described below.
For better separation of propanol, the conditions for dehydration refining of propanol in step (c-3) further comprise: the reflux ratio is 0.5-5.
The invention has no restriction on the vacuum distillation conditions in the step (c-4), as long as the extraction agent is recovered; preferably, the vacuum distillation conditions in step (c-4) include: the vacuum distillation temperature is 128-180 ℃. The vacuum distillation temperature refers to the bottom temperature of the sixth distillation column described below.
In order to better separate the extractant from the water, the vacuum distillation conditions in the step (c-4) further comprise: the reflux ratio is 0.1-3, and the operation condition is 50-10 kPa.
The invention has no limitation on the types of the extracting agent I and the extracting agent II, as long as the ethanol or the propanol is separated out; preferably, the extractant I and the extractant II are respectively and independently selected from at least one of ethylene glycol, dimethyl sulfoxide, N-methyl pyrrolidone and ethylene glycol.
In a preferred embodiment of the present invention, the extractant I and the extractant II are the same, and the obtained extractant solution contains only one extractant, and can be recycled for use in the processes of ethanol dehydration purification, partial dehydration of propanol or propanol dehydration purification. According to the invention, the same extractant is adopted in the extraction process of ethanol and propanol, so that the recovery of the extractant in the subsequent step (c-4) can be carried out in one recovery device.
Preferably, the water content of the propanol solution I is 4-8 wt%;
preferably, the water content of the propanol solution II is 20-28 wt%.
According to a preferred embodiment of the present invention, the refining separation of step (c) comprises the following processes:
(c-1) contacting the mixed solution I with an extracting agent I to perform ethanol extraction rectification to obtain an absolute ethanol product and a mixed solution II;
the dehydration refining conditions comprise: the ethanol extraction temperature is 72-80 ℃, the reflux ratio is 0.2-5, and the mass ratio of the extractant I to the mixed solution I is 0.5-7;
(c-2) contacting the mixed solution II with an extracting agent II to perform propanol extraction and rectification to obtain a water-containing propanol solution I and a mixed solution III;
the dehydration conditions include: the extraction temperature of the propanol is 85-95 ℃, and the reflux ratio is 0.2-5;
(c-3) dehydrating and refining the propanol solution I to obtain the anhydrous propanol product and a water-containing propanol solution II; refluxing the propanol solution II to the step (c-2), and adding the propanol solution II into the mixed solution II;
the conditions for dehydrating and refining the propanol comprise: the dehydration temperature of the propanol is 90-100 ℃, and the reflux ratio is 0.5-5;
(c-4) carrying out reduced pressure rectification on the mixed solution III to recover an extracting agent to obtain the wastewater I and an extracting agent solution, and recycling the extracting agent solution for the step (c-2);
the vacuum rectification conditions comprise: the temperature I is 128 ℃ and 180 ℃, the reflux ratio is 0.1-3, and the operation condition is 50-10 kPa.
In a preferred embodiment of the present invention, the step (d) comprises the following processes:
(d-1) carrying out mixed alcohol extraction and concentration on the water phase material flow to obtain the wastewater II and the material flow containing organic matters;
and (3) carrying out phase separation on the organic matter-containing material flow to obtain an upper oil phase I and a lower water phase I, refluxing the lower water phase I in the step (d-1) and adding the lower water phase I into the water phase material flow, and refluxing the upper oil phase I in the step (b) and adding the upper oil phase I into the two-phase solution.
The present invention has no limitation on the conditions for the concentration of the mixed alcohol in the step (d-1), as long as the aforementioned product is obtained; preferably, the alcohol-mixing concentration conditions in step (d-1) include: the concentration temperature of mixed alcohol is 98-110 ℃. The organic matter can be better separated from the aqueous phase stream by adopting the preferred scheme of the invention. The concentration temperature of the mixed alcohol refers to the tower bottom temperature of the seventh rectifying tower.
Preferably, the alcohol-mixing concentration condition in the step (d-1) further comprises: the reflux ratio is 0.1-3.
In a preferred embodiment of the present invention, the step (d) further comprises the following process:
(d-2) carrying out alcohol mixing dehydration refining on the oil phase material flow to obtain an anhydrous alcohol mixing product and wastewater III;
and (3) carrying out phase splitting on the wastewater III to obtain an upper oil phase II and a lower water phase II, refluxing the upper oil phase II to the step (d-2) and adding the upper oil phase II into the oil phase material flow, and refluxing the lower water phase II to the step (b) and adding the lower water phase II into the two-phase solution.
The present invention is not limited to the conditions for the dehydration purification of the mixed alcohol in the step (d-2) as long as the aforementioned product can be obtained; preferably, the conditions for dehydration and purification of the mixed alcohol in the step (d-2) include: the dehydration temperature of the mixed alcohol is 100-180 ℃. The mixed alcohol can be better separated from the oil phase stream by adopting the preferred scheme of the invention. The mixed alcohol dehydration temperature refers to the bottom temperature of the eighth rectifying tower.
Preferably, the conditions for dehydration and refining of the mixed alcohol in the step (d-2) further include: the reflux ratio is 0.01-3.
According to a preferred embodiment of the present invention, the step (d) comprises the following processes:
(d-1) carrying out mixed alcohol extraction and concentration on the water phase material flow to obtain the wastewater II and the material flow containing organic matters; the rectification dehydration conditions comprise: the concentration temperature of mixed alcohol is 98-110 ℃, and the reflux ratio is 0.1-3;
carrying out phase separation on the organic matter-containing material flow to obtain an upper oil phase I and a lower water phase I, refluxing the lower water phase I in the step (d-1) and adding the lower water phase I into the water phase material flow, and refluxing the upper oil phase I in the step (b) and adding the upper oil phase I into the two-phase solution;
(d-2) carrying out alcohol mixing dehydration refining on the oil phase material flow to obtain an anhydrous alcohol mixing product and wastewater III; the conditions for dehydration and refining of the mixed alcohol comprise: the dehydration temperature of the mixed alcohol is 100-180 ℃, and the reflux ratio is 0.01-3;
and (3) carrying out phase splitting on the wastewater III to obtain an upper oil phase II and a lower water phase II, refluxing the upper oil phase II to the step (d-2) and adding the upper oil phase II into the oil phase material flow, and refluxing the lower water phase II to the step (b) and adding the lower water phase II into the two-phase solution.
According to a preferred embodiment provided by the invention, the method for separating and recovering non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis water comprises the following steps:
(a) concentrating the Fischer-Tropsch synthesis water by using a non-acidic oxygen-containing organic substance to obtain organic acid-containing wastewater and a non-acidic oxygen-containing organic substance aqueous solution;
the non-acidic oxygen-containing organic matter concentration conditions comprise: the concentration temperature of the non-acidic oxygen-containing organic matter is 65-90 ℃; the reflux ratio is 2-8;
(b) cutting the non-acidic oxygen-containing organic matter aqueous solution to obtain a crude methanol product, a two-phase solution and a mixed solution I; then, carrying out phase separation on the two-phase solution to obtain a water phase material flow and an oil phase material flow;
the process of segmentation includes two stages of temperature control: the first stage temperature is 40-75 ℃, and the second stage temperature is 75-85 ℃; the conditions for the segmentation include: the reflux ratio is 8-20; the vapor phase distribution ratio in the process of cutting the non-acidic oxygen-containing organic matter aqueous solution is 0.5-3, and the liquid phase distribution ratio is 0.5-2.5;
(c) the method comprises the following steps:
(c-1) contacting the mixed solution I with an extracting agent I to perform ethanol extraction rectification to obtain an absolute ethanol product and a mixed solution II; the ethanol extraction and rectification conditions comprise: the ethanol extraction temperature is 72-80 ℃, the reflux ratio is 0.2-5, and the mass ratio of the extractant I to the mixed solution I is 0.5-7;
(c-2) contacting the mixed solution II with an extracting agent II to perform propanol extraction and rectification to obtain a water-containing propanol solution I and a mixed solution III; the conditions of the propanol extractive distillation comprise: the extraction temperature of the propanol is 85-95 ℃, and the reflux ratio is 0.2-5;
(c-3) dehydrating and refining the propanol solution I to obtain the anhydrous propanol product and a water-containing propanol solution II; refluxing the propanol solution II to the step (c-2), and adding the propanol solution II into the mixed solution II; the conditions for dehydrating and refining the propanol comprise: the dehydration temperature of the propanol is 90-100 ℃, and the reflux ratio is 0.5-5;
(c-4) carrying out reduced pressure rectification on the mixed solution III to recover an extracting agent to obtain the wastewater I and an extracting agent solution, and recycling the extracting agent solution for the step (c-2); the vacuum rectification conditions comprise: the vacuum distillation temperature is 128-180 ℃, the reflux ratio is 0.1-3, and the operation condition is 50-10 kPa;
(d) the method comprises the following steps:
(d-1) carrying out mixed alcohol extraction and concentration on the water phase material flow to obtain the wastewater II and the material flow containing organic matters; the mixed alcohol concentration conditions comprise: the concentration temperature of mixed alcohol is 98-110 ℃, and the reflux ratio is 0.1-3;
carrying out phase separation on the organic matter-containing material flow to obtain an upper oil phase I and a lower water phase I, refluxing the lower water phase I in the step (d-1) and adding the lower water phase I into the water phase material flow, and refluxing the upper oil phase I in the step (b) and adding the upper oil phase I into the two-phase solution;
(d-2) carrying out alcohol mixing dehydration refining on the oil phase material flow to obtain an anhydrous alcohol mixing product and wastewater III; the conditions for dehydration and refining of the mixed alcohol comprise: the dehydration temperature of the mixed alcohol is 100-180 ℃, and the reflux ratio is 0.01-3;
and (3) carrying out phase splitting on the wastewater III to obtain an upper oil phase II and a lower water phase II, refluxing the upper oil phase II to the step (d-2) and adding the upper oil phase II into the oil phase material flow, and refluxing the lower water phase II to the step (b) and adding the lower water phase II into the two-phase solution.
The method can effectively realize Fischer-Tropsch synthesis water treatment aiming at Fischer-Tropsch synthesis water generated under different working conditions, such as low-temperature Fischer-Tropsch synthesis water or high-temperature Fischer-Tropsch synthesis water, and can obtain a crude methanol product, an absolute ethanol product, an absolute propanol product, an absolute alcohol-mixed product with high value of more than C3, wastewater I and wastewater II, wherein the wastewater I and the wastewater II can be further subjected to subsequent organic acid recovery, and can also be recycled to a synthesis gas preparation stage for water supplement of slurry prepared by rolling solid fuels such as coal and the like.
The method for separating and recovering the non-acidic oxygen-containing organic matters in the Fischer-Tropsch synthesis water can better improve the recovery rate, ensure the purity of the obtained product to be higher and simplify the whole separation and recovery process.
The invention provides a separation and recovery system of non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis water, which comprises a first rectifying tower and a bulkhead rectifying tower; the bulkhead rectifying tower is provided with a lateral line extraction unit, and the lateral line extraction unit is externally connected with a rectifying mechanism I; a discharge hole at the bottom of the bulkhead rectifying tower is communicated with a first phase separator through a pipeline, and the first phase separator is communicated with a rectifying mechanism II;
the first rectifying tower is used for concentrating Fischer-Tropsch synthesis water to obtain organic acid-containing wastewater and a non-acidic oxygen-containing organic matter aqueous solution;
the side-draw unit is used for side-draw to obtain a mixed solution I;
the rectification mechanism I is used for respectively refining and separating ethanol and propanol from the mixed solution I;
and the rectifying mechanism II is used for concentrating and refining the mixed alcohol obtained by phase separation of the first phase separator.
In the present invention, the structures of the first rectifying tower, the bulkhead rectifying tower, the rectifying mechanism i, the first phase separator, and the rectifying mechanism ii are not particularly limited as long as the corresponding objects of the present invention can be achieved.
Preferably, the theoretical plate number of the first rectifying tower is 20-60, and the feeding position of the Fischer-Tropsch synthesis water is 1/5-4/5 of the theoretical plate number. The preferred scheme of the invention is beneficial to concentrating the Fischer-Tropsch synthesis water and separating the oxygen-containing organic matters from the Fischer-Tropsch synthesis water.
In the invention, the calculation and feeding positions of the theoretical plates or the positions of the feeding plates are all the theoretical plates calculated from the top to the bottom of the tower.
In a preferred embodiment of the invention, in order to better play the role of the bulkhead rectifying tower in dividing the non-acidic oxygen-containing organic matter aqueous solution into the three streams, the total number of theoretical plates of the bulkhead rectifying tower is 40-100, the number of theoretical plates of the public rectifying section part positioned at the upper part of the vertical partition of the bulkhead rectifying tower accounts for 1/7-3/7 of the total number of theoretical plates, and the number of theoretical plates of the public stripping section part positioned at the lower part of the vertical partition accounts for 1/7-2/7 of the total number of theoretical plates; in the bulkhead rectifying tower, the number of theoretical plates at the position of the feed plate of the non-acidic oxygen-containing organic matter aqueous solution is 1/6-3/4 of the number of theoretical plates of the vertical partition, and the number of theoretical plates at the discharge position of the side draw unit is 1/4-4/5 of the number of theoretical plates of the vertical partition.
The bulkhead rectifying tower of the invention is conventional equipment in the field, and the bulkhead rectifying tower structure comprises: the tower top is provided with a condenser and a reflux and extraction loop in a conventional way, and can extract material flow at the tower top and adjust reflux ratio; the tower bottom is provided with a reboiler which can provide heat for the evaporation of the liquid in the whole rectification system; the middle part in the tower body is provided with a vertical clapboard, and the two sides of the vertical clapboard are respectively a pre-fractionation side and a main tower side; the feed inlet is positioned at the side of the pre-fractionation, and the side draw outlet is positioned at the side of the main tower.
In the bulkhead rectifying tower, the common rectifying section part at the upper part of the vertical clapboard comprises a part at the upper part of the vertical clapboard in the tower and a condenser which is arranged conventionally at the top of the tower, and the common stripping section part at the lower part of the vertical clapboard comprises a part at the lower part of the vertical clapboard in the tower and a reboiler which is arranged conventionally at the bottom of the tower.
In a preferred embodiment of the invention, the rectification mechanism i comprises a third rectification tower, a fourth rectification tower and a sixth rectification tower which are sequentially arranged, the third rectification tower is used for extracting and recovering ethanol, the fourth rectification tower is used for rectifying and recovering propanol, and the sixth rectification tower is used for rectifying and recovering an extractant. By adopting the preferred scheme of the invention, the process of separating the absolute ethyl alcohol and the absolute propyl alcohol can be simplified, and the separation recovery rate of the absolute ethyl alcohol and the absolute propyl alcohol can be improved.
In order to better separate and recover the anhydrous propanol, a fifth rectifying tower is communicated between the fourth rectifying tower and the sixth rectifying tower and is used for further dehydrating and refining the propanol.
In a preferred embodiment of the present invention, the number of theoretical plates of the third distillation column is 25 to 60, the feeding position of the raw material is 2/5 to 4/5 of the number of theoretical plates, and the feeding position of the extractant I is 1/6 to 1/3 of the number of theoretical plates.
Preferably, the theoretical plate number of the fourth rectifying tower is 25-60, the feeding position of raw materials is 3/5-5/6 of the theoretical plate number, and the feeding position of extractant II is 1/6-2/5 of the theoretical plate number.
Preferably, the theoretical plate number of the sixth rectifying tower is 8-40, and the raw material feeding position is 1/4-3/4 of the theoretical plate number.
Preferably, the theoretical plate number of the fifth rectifying tower is 15-50, and the raw material feeding position is 1/7-4/7 of the theoretical plate number.
In a preferred embodiment of the present invention, the rectification unit ii includes a seventh rectification column and an eighth rectification column, which are respectively communicated with the first phase separator, the seventh rectification column is configured to concentrate the aqueous phase material flow obtained by phase separation in the first phase separator, and the eighth rectification column is configured to perform mixed alcohol dehydration refining on the oil phase material flow obtained by phase separation in the first phase separator. The mixed alcohol can be better dehydrated by adopting the preferred scheme of the invention.
In order to fully exert the advantages of the matching use of phase separation and rectification, the rectification tower T7The second phase separator is communicated with the first phase separator and is used for transmitting an upper oil phase I obtained by phase separation of the second phase separator to the first phase separator.
Preferably, the eighth rectifying tower is communicated with a third phase separator, and the third phase separator is communicated with the first phase separator and is used for transmitting the lower-layer water phase II obtained by phase separation of the third phase separator to the first phase separator.
Preferably, said rectification column T7The number of theoretical plates is 10-40, and the feeding position of raw materials is 1/4-3/4 of the number of theoretical plates; the theoretical plate number of the eighth rectifying tower is 15-40, and the raw material feeding position is 1/15-2/3 of the theoretical plate number.
According to a specific preferred embodiment provided by the invention, the separation and recovery system for non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis water comprises a first rectifying tower and a dividing wall rectifying tower; the dividing wall rectifying tower is provided with a side line extraction unit, the side line extraction unit is externally connected with a rectifying mechanism I, the rectifying mechanism I comprises a third rectifying tower, a fourth rectifying tower and a sixth rectifying tower which are sequentially arranged, and a fifth rectifying tower is communicated between the fourth rectifying tower and the sixth rectifying tower; the discharge hole at the bottom of the dividing wall rectifying tower passes through a pipeThe channel is communicated with a first phase separator, the first phase separator is communicated with a rectification mechanism II, the rectification mechanism II comprises a seventh rectification tower and an eighth rectification tower which are respectively communicated with the first phase separator, and the rectification tower T7The second phase separator is communicated with the first phase separator, the eighth rectifying tower is communicated with a third phase separator, and the third phase separator is communicated with the first phase separator;
the first rectifying tower is used for concentrating Fischer-Tropsch synthesis water to obtain organic acid-containing wastewater and a non-acidic oxygen-containing organic matter aqueous solution; the theoretical plate number of the first rectifying tower is 20-60, and the feeding position of the Fischer-Tropsch synthesis water is 1/5-4/5 of the theoretical plate number;
the side-draw unit is used for side-draw to obtain a mixed solution I; the total number of theoretical plates of the bulkhead rectifying tower is 40-100, the number of the theoretical plates of the public rectifying section part positioned at the upper part of the vertical partition of the bulkhead rectifying tower accounts for 1/7-3/7 of the total number of the theoretical plates, and the number of the theoretical plates of the public stripping section part positioned at the lower part of the vertical partition is 1/7-2/7 of the total number of the theoretical plates; in the bulkhead rectifying tower, the number of theoretical plates at the position of the feed plate of the non-acidic oxygen-containing organic matter aqueous solution is 1/6-3/4 of the number of theoretical plates of the vertical partition, and the number of theoretical plates at the discharge position of the side draw unit is 1/4-4/5 of the number of theoretical plates of the vertical partition;
the rectifying mechanism I is used for refining and separating ethanol and propanol from the mixed solution I respectively, the number of theoretical plates of the third rectifying tower is 25-60, the feeding position of a raw material is 2/5-4/5 of the number of the theoretical plates, and the feeding position of an extracting agent I is 1/6-1/3 of the number of the theoretical plates; the number of theoretical plates of the fourth rectifying tower is 25-60, the feeding position of the raw material is 3/5-5/6 of the number of the theoretical plates, and the feeding position of the extractant II is 1/6-2/5 of the number of the theoretical plates; the theoretical plate number of the sixth rectifying tower is 8-40, and the raw material feeding position is 1/4-3/4 of the theoretical plate number; the theoretical plate number of the fifth rectifying tower is 15-50, and the raw material feeding position is 1/7-4/7 of the theoretical plate number;
the rectifying mechanism II is used for concentrating and refining the mixed alcohol obtained by phase splitting of the first phase splitter, and the rectifying tower T7The number of theoretical plates is 10-40, and the feeding position of raw materials is 1/4-3/4 of the number of theoretical plates; the theoretical plate number of the eighth rectifying tower is 15-40, and the raw material feeding position is 1/15-2/3 of the theoretical plate number.
Compared with the prior art, on one hand, the separation and recovery system provided by the invention can realize the purpose of mixed alcohol dehydration and refining and avoid the use of an entrainer or an extractant due to the matched use of the bulkhead rectifying tower and the rectifying mechanism II and the phase separator, thereby avoiding the introduction of new impurities and saving energy consumption and a solvent recovery device; on the other hand, the method is simplified and easy to control, and can obtain high recovery rate.
For a better understanding of the process and separation recovery system of the present invention, reference is now made to FIG. 1, which shows in a preferred embodiment of the invention, as shown in FIG. 1, a process of the present invention comprising:
(a) firstly, introducing Fischer-Tropsch synthesis water 1 into a first rectifying tower T1 to concentrate non-acidic oxygen-containing organic matters, obtaining a non-acidic oxygen-containing organic matter water solution 2 at the top of the first rectifying tower T1, and obtaining organic acid-containing wastewater 3 at the bottom of the tower;
(b) introducing the non-acidic oxygen-containing organic matter-containing aqueous solution 2 into a bulkhead rectifying tower T2 for rectifying and dividing, obtaining a crude methanol product 4 at the tower top, obtaining a mixed solution I5 by side line extraction, and obtaining a two-phase solution 6 at the tower bottom; then introducing the two-phase solution 6 into a first phase separator T9 for phase separation to obtain a water-phase material flow 17 and an oil-phase material flow 20;
(c) introducing the mixed solution I5 into a third rectifying tower T3, contacting with an extracting agent I7 to perform ethanol extraction rectification, obtaining an absolute ethanol product 8 at the tower top, and obtaining a mixed solution II 9 at the tower bottom;
introducing the mixed solution II 9 into a fourth rectifying tower T4, contacting with an extracting agent II 10 to perform propanol extraction rectification, obtaining a water-containing propanol solution I11 at the tower top, and obtaining a mixed solution III 12 at the tower bottom;
introducing the propanol solution I11 into a fifth rectifying tower T5, dehydrating and refining propanol to obtain an anhydrous propanol product 14 at the bottom of the tower and a hydrous propanol solution II 13 at the top of the tower; refluxing the propanol solution II 13 to a fourth rectifying tower T4;
introducing the mixed solution III 12 into a sixth rectifying tower T6, carrying out reduced pressure rectification to recover an extracting agent, obtaining wastewater I15 at the tower top, obtaining an extracting agent solution 16 at the tower bottom, and recycling the extracting agent solution 16 in the step (c);
(d) introducing the water-phase material flow 17 into a seventh rectifying tower T7, carrying out mixed alcohol extraction and concentration, obtaining waste water II 19 at the tower bottom, and obtaining an organic material-containing material flow at the tower top; introducing the organic matter-containing material flow into a second phase separator T10 for phase separation to obtain an upper oil phase I18 and a lower water phase I, refluxing the lower water phase I into a seventh rectifying tower T7, and refluxing the upper oil phase I18 into the first phase separator T9;
introducing the oil phase material flow 20 into an eighth rectifying tower T8, performing mixed alcohol dehydration and refining, obtaining an anhydrous mixed alcohol product 22 at the tower bottom, and obtaining wastewater III at the tower top; and (3) introducing the wastewater III into a third phase separator T11 for phase separation to obtain an upper oil phase II and a lower water phase II 21, refluxing the upper oil phase II into an eighth rectifying tower T8, and refluxing the lower water phase II 21 into the first phase separator T9.
The present invention will be described in detail below by way of examples. In the following examples, the starting materials were all commercially available products unless otherwise specified. In the following examples, the composition of each stream and the purity of each product were routinely tested by gas chromatography.
Example 1
This example illustrates the process and separation recovery system of the present invention.
As shown in fig. 1, the separation and recovery method comprises:
(a) firstly, introducing low-temperature Fischer-Tropsch synthesis water 1 (the composition of which is shown in Table 1) into a first rectifying tower T1 to concentrate non-acidic oxygen-containing organic matters, wherein the number of theoretical plates of the tower is 36, the feeding position is a 22 th theoretical plate, the reflux ratio is 6.5, the temperature at the top of the tower is controlled to be 75.9 ℃, a non-acidic oxygen-containing organic matter aqueous solution 2 rich in aldehydes, ketones, esters and alcohol compounds is obtained at the top of the first rectifying tower T1, and organic acid-containing wastewater 3 is obtained at the bottom of the tower;
(b) introducing the non-acidic oxygen-containing organic matter aqueous solution 2 into a bulkhead rectifying tower T2 for rectification and segmentation, wherein the total number of theoretical plates of the bulkhead rectifying tower T2 is 61, the number of theoretical plates of a public rectifying section part positioned at the upper part of a vertical partition plate is 20, the number of theoretical plates of a public stripping section part positioned at the lower part of the vertical partition plate is 11, a feed plate is positioned on a 12 th theoretical plate at a pre-rectifying side, a side draw outlet is positioned on a 16 th theoretical plate at a main tower side, the reflux ratio is 16, the vapor phase distribution ratio (the pre-rectifying side is larger than the main tower side) is 2.57, the liquid phase distribution ratio (the pre-rectifying side is larger than the main tower side) is 1.5, the tower top temperature is controlled to be 60.8 ℃, the side draw temperature is 79.4 ℃, a crude methanol product 4 mainly comprising methanol, acetaldehyde, acetone, methyl acetate, ethyl acetate and a small amount of ethanol is obtained at the tower top, and the crude methanol product 4 can be used as fuel, Acetaldehyde, acetone and other products are extracted at the side line to obtain a mixed solution I5 of ethanol, propanol and water, and a two-phase solution 6 mainly comprising butanol, pentanol, hexanol and water is obtained at the bottom of the tower;
then the two-phase solution 6 is fed into a first phase separator T9 for phase separation, the lower layer obtains a water phase material flow 17 containing trace mixed alcohol with more than C3, and the upper layer obtains an oil phase material flow 20 which mainly contains the mixed alcohol with more than C3;
(c) introducing the mixed solution I5 into a third rectifying tower T3, contacting with an extractant I7 to perform ethanol extractive rectification, wherein the number of theoretical plates of the third rectifying tower T3 is 40, the feeding position of the mixed solution I5 is a 22 th theoretical plate, the feeding position of the extractant is a 5 th theoretical plate, the extractant I7 is ethylene glycol, the mass ratio of the ethylene glycol to the mixed solution I5 is 1.38, the temperature at the top of the tower is controlled to be 77.9 ℃, the reflux ratio is 3, an anhydrous ethanol product 8 is obtained at the top of the tower, and a mixed solution II 9 mainly comprising the extractant, propanol and water is obtained at the bottom of the tower;
introducing the mixed solution II 9 into a fourth rectifying tower T4, contacting with an extractant II 10 to perform propanol extractive rectification, wherein the number of theoretical plates of the fourth rectifying tower T4 is 40, the feeding position of the mixed solution II 9 is a 34 th theoretical plate, the extractant II 10 is ethylene glycol, the feeding position of the ethylene glycol is a 4 th plate, the mass ratio of the ethylene glycol to the mixed solution II 9 is 4.79, the temperature at the top of the tower is controlled to be 92.1 ℃, the reflux ratio is 1, a propanol solution I11 containing 5 wt% of water is obtained at the top of the tower, and a mixed solution III 12 mainly containing the extractant and the water is obtained at the bottom of the tower;
introducing the propanol solution I11 into a fifth rectifying tower T5 for dehydration and refining of propanol, wherein the number of theoretical plates of the fifth rectifying tower T5 is 20, the feeding position of the propanol solution I11 is a 3 rd theoretical plate, the temperature of the tower bottom is controlled to be 97.1 ℃, the reflux ratio is 1.5, an anhydrous propanol product 14 is obtained at the tower bottom, and a water-containing propanol solution II 13 is obtained at the tower top; refluxing the propanol solution II 13 to a fourth rectifying tower T4;
introducing the mixed solution III 12 into a sixth rectifying tower T6, carrying out reduced pressure rectification to recover an extractant, wherein the number of theoretical plates of the sixth rectifying tower T6 is 14, the feeding position of the mixed solution III 12 is a 7 th theoretical plate, the reflux ratio is 0.7, the operating pressure is 10kPa, the temperature at the bottom of the tower is controlled at 132.7 ℃, waste water I15 is obtained at the top of the tower, an extractant solution 16 is obtained at the bottom of the tower, and the extractant solution 16 is recycled in the step (c);
(d) introducing the water-phase material flow 17 into a seventh rectifying tower T7, and carrying out mixed alcohol concentration, wherein the number of theoretical plates of the seventh rectifying tower T7 is 20, the feeding position is a 9 th theoretical plate, the reflux ratio is 0.2, the temperature of the tower bottom is controlled to be 100 ℃, waste water II 19 is obtained at the tower bottom, and the material flow containing organic matters is obtained at the tower top;
introducing the organic matter-containing material flow into a second phase separator T10 for phase separation to obtain an upper oil phase I18 and a lower water phase I, refluxing the lower water phase I into a seventh rectifying tower T7, and refluxing the upper oil phase I18 into the first phase separator T9;
introducing the oil phase material flow 20 into an eighth rectifying tower T8, and performing mixed alcohol dehydration and refining, wherein the number of theoretical plates of the eighth rectifying tower T8 is 25, the feeding position is a 2 nd theoretical plate, the reflux ratio is 0.01, the temperature of the tower bottom is controlled to be 126.5 ℃, an anhydrous mixed alcohol product 22 is obtained at the tower bottom, and wastewater III is obtained at the tower top; and (3) introducing the wastewater III into a third phase separator T11 for phase separation to obtain an upper oil phase II and a lower water phase II 21, refluxing the upper oil phase II into an eighth rectifying tower T8, and refluxing the lower water phase II 21 into the first phase separator T9.
The composition of the various streams in the above process is given in table 1 and the purity of the final product obtained is given in table 2.
Table 1 composition of the various streams (% by mass)
Figure BDA0002464354790000231
Figure BDA0002464354790000241
Example 2
This example illustrates the process and separation recovery system of the present invention.
As shown in fig. 1, the separation and recovery method comprises:
(a) firstly, introducing high-temperature Fischer-Tropsch synthesis water 1 (the composition of which is shown in Table 3) into a first rectifying tower T1 to concentrate non-acidic oxygen-containing organic matters, wherein the number of theoretical plates of the tower is 34, the feeding position is a 20 th theoretical plate, the reflux ratio is 8, the temperature at the top of the tower is controlled to be 71.6 ℃, a non-acidic oxygen-containing organic matter aqueous solution 2 rich in aldehydes, ketones and alcohol compounds is obtained at the top of the first rectifying tower T1, and organic acid-containing wastewater 3 is obtained at the bottom of the tower;
(b) introducing the water solution 2 containing the non-acidic oxygen-containing organic matters into a bulkhead rectifying tower T2 for rectification and segmentation, wherein the total number of theoretical plates of the bulkhead rectifying tower T2 is 65, the number of theoretical plates of a public rectifying section part positioned at the upper part of a vertical partition is 22, the number of theoretical plates of a public stripping section part positioned at the lower part of the vertical partition is 13, a feed plate is positioned at the 13 th theoretical plate of a pre-rectifying side, a side draw outlet is positioned at the 13 th theoretical plate of a main tower side, the reflux ratio is 16.8, the vapor phase distribution ratio (the pre-rectifying side is larger than the main tower side) is 2.33, the liquid phase distribution ratio (the pre-rectifying side is larger than the main tower side) is 0.96, the tower top temperature is controlled to be 42 ℃, the side draw temperature is 79.4 ℃, a crude methanol product 4 mainly comprising methanol, acetaldehyde, acetone, methyl acetate, ethyl acetate and a small amount of ethanol is obtained at the tower top, and the crude methanol product 4 can be used as a fuel, Acetaldehyde, acetone and other products are extracted at the side line to obtain a mixed solution I5 of ethanol, propanol and water, and a two-phase solution 6 mainly comprising butanol, pentanol, hexanol and water is obtained at the bottom of the tower;
then the two-phase solution 6 is fed into a first phase separator T9 for phase separation, the lower layer obtains a water phase material flow 17 containing trace mixed alcohol with more than C3, and the upper layer obtains an oil phase material flow 20 which mainly contains the mixed alcohol with more than C3;
(c) introducing the mixed solution I5 into a third rectifying tower T3, contacting with an extractant I7 to perform ethanol extractive rectification, wherein the number of theoretical plates of the third rectifying tower T3 is 42, the feeding position of the mixed solution I5 is 23 th theoretical plate, the feeding position of the extractant is 5 th theoretical plate, the extractant I7 is ethylene glycol, the mass ratio of the ethylene glycol to the mixed solution I5 is 1.25, the temperature at the top of the tower is controlled to be 77.8 ℃, the reflux ratio is 2.8, an anhydrous ethanol product 8 is obtained at the top of the tower, and a mixed solution II 9 mainly containing the extractant, propanol and water is obtained at the bottom of the tower;
introducing the mixed solution II 9 into a fourth rectifying tower T4, contacting with an extractant II 10 to perform propanol extractive rectification, wherein the number of theoretical plates of the fourth rectifying tower T4 is 38, the feeding position of the mixed solution II 9 is a 32 th theoretical plate, the extractant II 10 is ethylene glycol, the feeding position of the ethylene glycol is a 4 th plate, the mass ratio of the ethylene glycol to the mixed solution II 9 is 4.25, the temperature at the top of the tower is controlled to be 92.2 ℃, the reflux ratio is 1, a propanol solution I11 containing 5 wt% of water is obtained at the top of the tower, and a mixed solution III 12 mainly containing the extractant and the water is obtained at the bottom of the tower;
introducing the propanol solution I11 into a fifth rectifying tower T5 for dehydration and refining of propanol, wherein the number of theoretical plates of the fifth rectifying tower T5 is 18, the feeding position of the propanol solution I11 is a 3 rd theoretical plate, the temperature of the tower bottom is controlled to be 97.2 ℃, the reflux ratio is 1.5, an anhydrous propanol product 14 is obtained at the tower bottom, and a water-containing propanol solution II 13 is obtained at the tower top; refluxing the propanol solution II 13 to a fourth rectifying tower T4;
introducing the mixed solution III 12 into a sixth rectifying tower T6, carrying out reduced pressure rectification to recover an extractant, wherein the number of theoretical plates of the sixth rectifying tower T6 is 15, the feeding position of the mixed solution III 12 is a 7 th theoretical plate, the reflux ratio is 1, the operating pressure is 10kPa, the temperature at the bottom of the tower is controlled to be 132.7 ℃, waste water I15 is obtained at the top of the tower, an extractant solution 16 is obtained at the bottom of the tower, and the extractant solution 16 is recycled in the step (c);
(d) introducing the water-phase material flow 17 into a seventh rectifying tower T7, and carrying out mixed alcohol concentration, wherein the number of theoretical plates of the seventh rectifying tower T7 is 22, the feeding position is a 10 th theoretical plate, the reflux ratio is 0.4, the temperature of the tower bottom is controlled to be 100 ℃, waste water II 19 is obtained at the tower bottom, and the material flow containing organic matters is obtained at the tower top;
introducing the organic matter-containing material flow into a second phase separator T10 for phase separation to obtain an upper oil phase I18 and a lower water phase I, refluxing the lower water phase I into a seventh rectifying tower T7, and refluxing the upper oil phase I18 into the first phase separator T9;
introducing the oil phase material flow 20 into an eighth rectifying tower T8, and performing mixed alcohol dehydration and refining, wherein the number of theoretical plates of the eighth rectifying tower T8 is 24, the feeding position is a 2 nd theoretical plate, the reflux ratio is 0.05, the temperature of the tower bottom is controlled to be 125 ℃, an anhydrous mixed alcohol product 22 is obtained at the tower bottom, and wastewater III is obtained at the tower top; and (3) introducing the wastewater III into a third phase separator T11 for phase separation to obtain an upper oil phase II and a lower water phase II 21, refluxing the upper oil phase II into an eighth rectifying tower T8, and refluxing the lower water phase II 21 into the first phase separator T9.
The composition of the various streams in the above process is given in table 3 and the purity of the final product obtained is given in table 4.
Table 3 composition of the various streams (% by mass)
Figure BDA0002464354790000261
Figure BDA0002464354790000271
TABLE 4 purity of the product recovered by separation
Figure BDA0002464354790000272
It can be seen from examples 1 and 2 and tables 1 to 4 that by using the method and the separation system of the present invention, separation and recovery of non-acidic oxygen-containing organic substances in high temperature fischer-tropsch synthesis water or low temperature fischer-tropsch synthesis water can be achieved, and a high purity crude methanol product, an anhydrous ethanol product, an anhydrous propanol product, an anhydrous mixed alcohol product and a wastewater product (including organic acid-containing wastewater, wastewater i and wastewater ii) can be obtained, wherein the purity is even up to 99.999 wt%, and the purity of the obtained wastewater product is more than 97.7 wt%.
When the method in the prior art is adopted, a high-purity crude methanol product, an anhydrous ethanol product, an anhydrous propanol product, an anhydrous alcohol-mixed product and a wastewater product cannot be obtained at the same time, and the purity is low.
When the technical scheme which is not in the range of the parameters of the invention, especially the technical scheme which is not in the range of the reflux ratio and the temperature of the invention is adopted, the products can not be obtained simultaneously, and the purity of the obtained product is relatively low, thus the technical effect of the invention shown by the examples 1-2 can not be achieved at all.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (16)

1. A method for separating and recovering non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis water is characterized by comprising the following steps:
(a) concentrating the Fischer-Tropsch synthesis water by using a non-acidic oxygen-containing organic substance to obtain organic acid-containing wastewater and a non-acidic oxygen-containing organic substance aqueous solution;
(b) cutting the non-acidic oxygen-containing organic matter aqueous solution to obtain a crude methanol product, a two-phase solution and a mixed solution I; then, carrying out phase separation on the two-phase solution to obtain a water phase material flow and an oil phase material flow;
(c) refining and separating the mixed solution I to obtain an absolute ethyl alcohol product, an absolute propyl alcohol product and wastewater I;
(d) and carrying out alcohol mixing concentration and alcohol mixing refining on the water phase material flow and the oil phase material flow to obtain an anhydrous alcohol mixing product and wastewater II.
2. The process of claim 1, wherein the conditions of the non-acidic oxygenate concentration in step (a) comprise: the concentration temperature of the non-acidic oxygen-containing organic matter is 65-90 ℃;
preferably, the conditions for the concentration of the non-acidic oxygen-containing organic substance in step (a) comprise: the reflux ratio is 2-8;
preferably, the water content of the non-acidic oxygen-containing organic matter aqueous solution is 25-35 wt%;
preferably, the non-acidic oxygen-containing organic substance aqueous solution contains at least one of aldehydes, ketones, esters, and alcohol compounds.
3. The method of claim 1 or 2, wherein the splitting in step (b) comprises two stages of temperature control: the first stage temperature is 40-75 ℃, and the second stage temperature is 75-85 ℃;
preferably, the conditions for the segmentation in step (b) include: the reflux ratio is 8-20;
preferably, the conditions for the segmentation in step (b) further comprise: the vapor phase distribution ratio in the process of cutting the non-acidic oxygen-containing organic matter aqueous solution is 0.5-3, and the liquid phase distribution ratio is 0.5-2.5;
preferably, the crude methanol product contains methanol and at least one of acetaldehyde, acetone, methyl acetate, ethyl acetate, and ethanol;
preferably, the two-phase solution contains at least one of butanol, pentanol, hexanol, and water.
4. The process of any one of claims 1 to 3 wherein the Fischer-Tropsch synthesis water contains from 1 to 15 wt% of oxygenated organics.
5. The method of any one of claims 1-4, wherein the polishing separation of step (c) comprises the following:
(c-1) contacting the mixed solution I with an extracting agent I to perform ethanol extraction rectification to obtain an absolute ethanol product and a mixed solution II;
(c-2) contacting the mixed solution II with an extracting agent II to perform propanol extraction and rectification to obtain a water-containing propanol solution I and a mixed solution III;
(c-3) dehydrating and refining the propanol solution I to obtain the anhydrous propanol product and a water-containing propanol solution II; optionally refluxing the propanol solution II to the step (c-2) and adding the propanol solution II into the mixed solution II;
and (c-4) carrying out reduced pressure rectification on the mixed solution III to obtain the wastewater I and an extractant solution.
6. The method of claim 5, wherein the ethanol extractive distillation conditions in step (c-1) comprise: the temperature of ethanol extraction is 72-80 ℃;
preferably, the ethanol extractive distillation conditions in step (c-1) further comprise: the reflux ratio is 0.2-5;
preferably, in the step (c-1), the mass ratio of the extracting agent I to the mixed solution I is 0.5-7;
preferably, the conditions for the extractive distillation of propanol in step (c-2) include: the extraction temperature of the propanol is 85-95 ℃;
preferably, the conditions for the extractive distillation of propanol in the step (c-2) further comprise: the reflux ratio is 0.2-5;
preferably, in the step (c-2), the mass ratio of the extracting agent II to the mixed solution II is 1-7;
preferably, the conditions for dehydrating and refining propanol in the step (c-3) include: the dehydration temperature of the propanol is 90-100 ℃;
preferably, the conditions for dehydrating and refining propanol in the step (c-3) further include: the reflux ratio is 0.5-5;
preferably, the vacuum distillation conditions in step (c-4) include: the vacuum distillation temperature is 128-180 ℃;
preferably, the vacuum distillation conditions in step (c-4) further comprise: the reflux ratio is 0.1-3, and the operation condition is 50-10 kPa.
7. The process of claim 5 or 6, wherein the extractant I and the extractant II are each independently selected from at least one of ethylene glycol, dimethyl sulfoxide, N-methylpyrrolidone, and ethylene glycol;
preferably, the extractant I and the extractant II are the same;
preferably, the water content of the propanol solution I is 4-8 wt%;
preferably, the water content of the propanol solution II is 20-28 wt%.
8. The method according to any one of claims 1-7, wherein the step (d) comprises the process of:
(d-1) carrying out mixed alcohol extraction and concentration on the water phase material flow to obtain the wastewater II and the material flow containing organic matters;
carrying out phase separation on the organic matter-containing material flow to obtain an upper oil phase I and a lower water phase I, refluxing the lower water phase I in the step (d-1) and adding the lower water phase I into the water phase material flow, and refluxing the upper oil phase I in the step (b) and adding the upper oil phase I into the two-phase solution;
preferably, the step (d) further comprises the following process:
(d-2) carrying out alcohol mixing dehydration refining on the oil phase material flow to obtain an anhydrous alcohol mixing product and wastewater III;
and (3) carrying out phase splitting on the wastewater III to obtain an upper oil phase II and a lower water phase II, refluxing the upper oil phase II to the step (d-2) and adding the upper oil phase II into the oil phase material flow, and refluxing the lower water phase II to the step (b) and adding the lower water phase II into the two-phase solution.
9. The method of claim 8, wherein the alcohol-mixing concentration conditions in step (d-1) comprise: mixing alcohol, extracting at 98-110 deg.C;
preferably, the alcohol-mixing concentration condition in the step (d-1) further comprises: the reflux ratio is 0.1-3;
preferably, the conditions for dehydration and purification of the mixed alcohol in the step (d-2) include: the dehydration temperature of the mixed alcohol is 100-180 ℃;
preferably, the conditions for dehydration and refining of the mixed alcohol in the step (d-2) further include: the reflux ratio is 0.01-3.
10. A separation and recovery system for non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis water is characterized by comprising a first rectifying tower and a bulkhead rectifying tower; the bulkhead rectifying tower is provided with a lateral line extraction unit, and the lateral line extraction unit is externally connected with a rectifying mechanism I; a discharge hole at the bottom of the bulkhead rectifying tower is communicated with a first phase separator through a pipeline, and the first phase separator is communicated with a rectifying mechanism II;
the first rectifying tower is used for concentrating non-acidic oxygen-containing organic matters in the Fischer-Tropsch synthesis water to obtain organic acid-containing wastewater and a non-acidic oxygen-containing organic matter aqueous solution;
the side-draw unit is used for side-draw to obtain a mixed solution I;
the rectification mechanism I is used for respectively refining and separating ethanol and propanol from the mixed solution I;
and the rectifying mechanism II is used for concentrating and refining the mixed alcohol obtained by phase separation of the first phase separator.
11. The separation and recovery system of claim 10, wherein the first rectification column has a theoretical plate number of 20 to 60, and the fischer-tropsch synthesis water is fed at a position of 1/5 to 4/5 of the theoretical plate number.
12. The separation and recovery system of claim 10 or 11, wherein the dividing wall distillation column has a total theoretical plate count of 40 to 100, the theoretical plate count of the common rectification section located in an upper portion of the vertical partition wall of the dividing wall distillation column is 1/7 to 3/7 of the total theoretical plate count, and the theoretical plate count of the common stripping section located in a lower portion of the vertical partition wall distillation column is 1/7 to 2/7 of the total theoretical plate count;
in the bulkhead rectifying tower, the number of theoretical plates at the position of the feed plate of the non-acidic oxygen-containing organic matter aqueous solution is 1/6-3/4 of the number of theoretical plates of the vertical partition, and the number of theoretical plates at the discharge position of the side draw unit is 1/4-4/5 of the number of theoretical plates of the vertical partition.
13. The separation and recovery system according to any one of claims 10 to 12, wherein the rectification mechanism i comprises a third rectification tower, a fourth rectification tower and a sixth rectification tower, which are arranged in sequence, the third rectification tower is used for extracting and recovering ethanol, the fourth rectification tower is used for rectifying and recovering propanol, and the sixth rectification tower is used for rectifying and recovering an extractant;
preferably, a fifth rectifying tower is communicated between the fourth rectifying tower and the sixth rectifying tower and is used for further dehydrating and refining the propanol.
14. The separation and recovery system of claim 13, wherein the third rectification column has a theoretical plate number of 25 to 60, a raw material feeding position of 2/5 to 4/5 of the theoretical plate number, and an extractant i feeding position of 1/6 to 1/3 of the theoretical plate number;
the number of theoretical plates of the fourth rectifying tower is 25-60, the feeding position of the raw material is 3/5-5/6 of the number of the theoretical plates, and the feeding position of the extractant II is 1/6-2/5 of the number of the theoretical plates;
the theoretical plate number of the sixth rectifying tower is 8-40, and the raw material feeding position is 1/4-3/4 of the theoretical plate number;
preferably, the theoretical plate number of the fifth rectifying tower is 15-50, and the raw material feeding position is 1/7-4/7 of the theoretical plate number.
15. The separation and recovery system according to any one of claims 10 to 14, wherein the rectification mechanism ii comprises a seventh rectification column and an eighth rectification column, which are respectively communicated with the first phase separator, the seventh rectification column is used for concentrating the aqueous phase stream obtained by phase separation in the first phase separator, and the eighth rectification column is used for performing mixed alcohol dehydration refining on the oil phase stream obtained by phase separation in the first phase separator;
preferably, said rectification column T7The second phase separator is communicated with the first phase separator and is used for transmitting an upper oil phase I obtained by phase separation of the second phase separator to the first phase separator;
preferably, the eighth rectifying tower is communicated with a third phase separator, and the third phase separator is communicated with the first phase separator and used for transmitting the lower-layer water phase II obtained by phase separation of the third phase separator to the first phase separator.
16. The separation and recovery system of claim 15, wherein the rectification column T7The number of theoretical plates is 10-40, and the feeding position of raw materials is 1/4-3/4 of the number of theoretical plates;
the theoretical plate number of the eighth rectifying tower is 15-40, and the raw material feeding position is 1/15-2/3 of the theoretical plate number.
CN202010329252.4A 2020-04-23 2020-04-23 Method and system for separating and recovering non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis water Pending CN111573761A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010329252.4A CN111573761A (en) 2020-04-23 2020-04-23 Method and system for separating and recovering non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis water

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010329252.4A CN111573761A (en) 2020-04-23 2020-04-23 Method and system for separating and recovering non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis water

Publications (1)

Publication Number Publication Date
CN111573761A true CN111573761A (en) 2020-08-25

Family

ID=72113100

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010329252.4A Pending CN111573761A (en) 2020-04-23 2020-04-23 Method and system for separating and recovering non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis water

Country Status (1)

Country Link
CN (1) CN111573761A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112679313A (en) * 2020-12-25 2021-04-20 国家能源集团宁夏煤业有限责任公司 Mixed alcohol separation system and mixed alcohol separation method
CN112707794A (en) * 2020-12-25 2021-04-27 国家能源集团宁夏煤业有限责任公司 Method for separating propanol from aqueous phase byproduct of Fischer-Tropsch synthesis

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110077366A1 (en) * 2008-06-03 2011-03-31 Solvay (Societe Anonyme) Process for the manufacture of at least one ethylene derivative compound
CN102093163A (en) * 2010-12-23 2011-06-15 上海兖矿能源科技研发有限公司 Method for separating and purifying ethanol from Tropsch synthesis reaction water
CN109796310A (en) * 2019-03-26 2019-05-24 河北工业大学 A method of initial gross separation being carried out to F- T synthesis water using next door rectifying column
CN110818531A (en) * 2019-11-12 2020-02-21 上海兖矿能源科技研发有限公司 Method for treating oxygen-containing organic matters in Fischer-Tropsch synthesis reaction water

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110077366A1 (en) * 2008-06-03 2011-03-31 Solvay (Societe Anonyme) Process for the manufacture of at least one ethylene derivative compound
CN102093163A (en) * 2010-12-23 2011-06-15 上海兖矿能源科技研发有限公司 Method for separating and purifying ethanol from Tropsch synthesis reaction water
CN109796310A (en) * 2019-03-26 2019-05-24 河北工业大学 A method of initial gross separation being carried out to F- T synthesis water using next door rectifying column
CN110818531A (en) * 2019-11-12 2020-02-21 上海兖矿能源科技研发有限公司 Method for treating oxygen-containing organic matters in Fischer-Tropsch synthesis reaction water

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
李春利等: "费托合成水中混合醇初步分离工艺的实验与模拟", 《煤炭学报》 *
武鹏等: "间接液化及产品加工成套技术开发研究进展", 《煤炭学报》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112679313A (en) * 2020-12-25 2021-04-20 国家能源集团宁夏煤业有限责任公司 Mixed alcohol separation system and mixed alcohol separation method
CN112707794A (en) * 2020-12-25 2021-04-27 国家能源集团宁夏煤业有限责任公司 Method for separating propanol from aqueous phase byproduct of Fischer-Tropsch synthesis
CN112707794B (en) * 2020-12-25 2022-11-08 国家能源集团宁夏煤业有限责任公司 Method for separating propanol from aqueous phase byproduct of Fischer-Tropsch synthesis

Similar Documents

Publication Publication Date Title
TWI421121B (en) Low-energy extractive distillation process for dehydration of aqueous ethanol
US5609734A (en) Combined distillation and permeation process for the separation of oxygenated compounds from hydrocarbons and use thereof in etherification
CN107074676B (en) Method for producing butadiene from ethanol in a low-water and low-energy reaction step
CN100575327C (en) Improved acetic acid purifying method
CN110372512B (en) Separation and purification process of dimethyl carbonate
CN108531342B (en) Production method and equipment for neutral edible brewed alcohol product
CN111377800B (en) Separation device and separation method for coal-to-ethanol liquid phase product
US8658845B2 (en) Process and adsorbent for separating ethanol and associated oxygenates from a biofermentation system
CN111573761A (en) Method and system for separating and recovering non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis water
CN107915612B (en) Method for preparing purified MIBK from industrial byproduct waste liquid acetone
CN111518593B (en) Method for primarily separating byproduct mixed alcohol in coal indirect liquefaction process
CN111100004A (en) Method and integrated device for refining dimethyl carbonate
CN102471194A (en) Method and system for producing methanol and dimethyl ether
CN111377801B (en) Method and system for refining low carbon alcohol
CN111499495B (en) Method for separating and recovering non-acidic oxygen-containing organic matters from Fischer-Tropsch synthesis water
WO2014097311A1 (en) Production of ethanol products
CN115028523A (en) Pressure-variable-heterogeneous azeotropic rectification separation method for butanone dehydration
CN107915615B (en) Method for preparing purified MIBK from industrial byproduct waste liquid acetone
CN1307109C (en) Method for recovering aromatic carboxylic acid in waste water
CN101812311A (en) Method for effectively refining tar anthracene oil and concentrating naphthalene
CN106187717B (en) The method for being thermally integrated variable-pressure rectification separation methyl tertiary butyl ether(MTBE) and methanol azeotrope
CN109734232B (en) Method for simultaneously recovering water and alcohol from Fischer-Tropsch synthesis wastewater
CN113429261B (en) System, method and application for separating and purifying ethanol from crude ethanol product
CN111087287B (en) Method for separating polymethoxy dimethyl ether
CN110878006B (en) Method and device for separating ethanol and ethyl acetate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20200825