CN110606609A - Method for recovering organic matters in F-T synthesis reaction water - Google Patents
Method for recovering organic matters in F-T synthesis reaction water Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- 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
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- 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
- C02F1/08—Thin film evaporation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
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- C—CHEMISTRY; METALLURGY
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- 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
Abstract
The invention relates to a method for recovering organic matters in F-T synthesis reaction water. The invention utilizes the property that anhydrous sodium sulfate is hydrated to generate stable crystalline hydrate, concentrates the organic matters in the F-T synthesis reaction water until the water content is less than 5 percent, reduces the material handling capacity of the organic matter recovery procedure in the subsequent working section by 85 to 90 percent, enables the separation method which can not be used due to overlarge energy consumption to be feasible, and greatly reduces the separation cost and the equipment investment; anhydrous sodium sulfate is dehydrated and converted into inorganic salt without crystal water at a lower temperature, and the inorganic salt is filtered and separated from the solution, so that the separated anhydrous salt is recycled, the concentration cost is reduced, and the economic benefit of an enterprise is improved; the water generated by the F-T synthesis reaction is recovered by utilizing the vacuum membrane distillation technology, so that the problem of serious unbalance of water balance of synthetic oil enterprises can be solved.
Description
Technical Field
The invention relates to a method for recovering organic matters in F-T synthesis reaction water.
Background
The core reaction of the Fischer-Tropsch (F-T) synthetic oil technology is the F-T synthetic reaction. In the F-T synthesis reaction, most of oxygen atoms in raw material synthesis gas CO are combined with hydrogen to generate water, and 1-1.3 tons of water are produced as a byproduct for producing 1 ton of hydrocarbon products. The reaction water of F-T synthesis contains a large amount of oxygen-containing organic matters, such as methanol, ethanol, acetone, acetaldehyde, formic acid, acetic acid and the like, and the composition and the content of the oxygen-containing organic matters in the reaction water obtained by different catalysts, different reaction temperatures and different reaction pressures are different, for example, the total amount of the organic matters in the synthesis water is up to 17.11 percent in the F-T synthesis process of Shanxi coal chemical industry, while the total amount of the organic matters in the synthesis water is only 3.33 percent in the low-temperature F-T synthesis oil process of Shanghai Yan mine.
The F-T synthesis reaction water contains rich oxygen-containing organic matters, and if the oxygen-containing organic matters are directly discharged without being treated, oxygen in the air can be prevented from being dissolved in the water, so that the oxygen deficiency of organisms in the water is dead, and the water quality is deteriorated. And moreover, oxygen-containing organic matters in the F-T synthesis reaction water are all organic chemical products with high added values, so that the organic chemical products have high economic values, and the recovery of the oxygen-containing organic matters has remarkable effects on increasing the product types of synthetic oil enterprises and improving the economic benefits of the enterprises. On the other hand, the water consumption of synthetic oil enterprises is very large, water resources are often relatively short in regions suitable for building large-scale F-T synthetic oil devices in China, oxygen-containing organic matters with high added values in F-T synthetic reaction water are separated, and the F-T synthetic reaction water is recycled, so that the method not only accords with the national industrial policy of water saving and emission reduction, but also can create good economic benefits and social benefits for the enterprises.
At present, a plurality of F-T synthesis reaction water recovery treatment technologies are developed at home and abroad, the domestic application effect is better by the Shanxi coal chemical institute water recovery technology, and the foreign application effect is better by the Sasol-I plant water recovery technology. The F-T synthesis reaction water treatment process developed by Shanxi coal gasification takes acetaldehyde, acetone, methanol, ethanol, butanol and organic acid as target products. Fractionating reaction water by a mixed acid cutting tower, distilling acetaldehyde, acetone, methanol, ethanol, n-propanol, n-butanol and the like from the tower top, and separating a mixed acid solution from the tower bottom, wherein the mixed acid solution contains 10-50% of water; the tower top fraction is subjected to multi-stage extraction and fractionation, and various alcohol, aldehyde and ketone products are separated and recovered; the mixed acid water solution at the bottom of the tower is extracted firstly, so that acetic acid, propionic acid, butyric acid and the like enter an extraction phase, and then acetic acid, propionic acid and butyric acid products with higher purity can be obtained through an extractant recovery tower, an acetic acid tower and a propionic acid tower. The water treatment and recovery process for F-T synthesis reaction in foreign Sasol-I factory has target products of methanol, ethanol, ketones, C3 and C4 (propanol, butanol, etc.) mixed alcohol. The process of Sasol-I plant is similar to that of Shanxi coal chemical, and the raw material reaction water is distilled, the distillate at the tower top is aqueous solution of alcohol, aldehyde, ketone and ester with 25% water content, and the aqueous solution of organic acid is at the tower bottom. The distillate at the tower top is subjected to gas stripping of a stripping tower, azeotropic distillation, hydroalcoholic treatment, dehydration of a dehydrating tower and other processes to recover oxygen-containing organic matters in reaction water in the forms of methanol, ethanol, mixed alcohol and the like. The organic acid water solution at the bottom of the primary fractionating tower is neutralized by alkali and then subjected to biochemical treatment.
The fischer-tropsch synthesis reaction produces higher hydrocarbons with the concomitant production of large amounts of water and small amounts of oxygenated organics such as methanol, ethanol, acetone, acetaldehyde, formic acid, acetic acid, and the like. Different F-T synthesis processes have different compositions and contents of oxygen-containing organic matters in the byproduct reaction water due to different catalysts and reaction conditions. The first step of the existing F-T synthesis reaction water treatment technology, which is a water treatment technology developed by coal gasification in Shanxi China or a F-T synthesis reaction water treatment recovery technology used by Sasol-I factory in south Africa, is to send raw material water into a fractionating tower and separate organic acid and other oxygen-containing organic matters by distillation. And obtaining an alcohol, aldehyde and ketone aqueous solution with the water content of 10-50% at the tower top, and obtaining the residual organic acid aqueous solution at the tower bottom. After the initial separation, the useful components are separated and recovered by adopting methods of multistage fractionation, extraction, hydroconversion, alkali addition neutralization and the like. The organic matter content in the F-T synthesis reaction water is 3.33-17.11%, and the rest 82.89-96.67% is water. In the subsequent treatment process of the water, the scale of the recovery treatment equipment is increased, the energy consumption in the subsequent treatment process is increased, and the investment cost and the operation cost of a post-treatment system are increased; in addition, the material treatment capacity is too large, and the useless components are too much, so that some treatment methods which are energy-consuming like freezing separation and evaporation separation are unavailable.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a method for recovering organic matters in F-T synthesis reaction water, which can concentrate the organic matters in the reaction water to a water content of less than 5% and reduce the material treatment capacity of the organic matter recovery procedure in the subsequent working section by 85% -90% so as to be beneficial to improving the separation effect, aiming at the current situation of the prior art.
The second technical problem to be solved by the invention is to provide a method for recovering organic matters in F-T synthesis reaction water, which can reduce the recovery cost, aiming at the current situation of the prior art.
The third technical problem to be solved by the invention is to provide a method for recovering organic matters in F-T synthetic reaction water, which is beneficial to stabilizing the water balance of synthetic oil enterprises, aiming at the current situation of the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for recovering organic matters in F-T synthesis reaction water is characterized by comprising the following steps: comprises the following steps
Feeding reaction water from the F-T synthetic wastewater filter into a sodium sulfate primary hydration reactor, and adding anhydrous sodium sulfate into the primary hydration reactor to hydrate the anhydrous sodium sulfate and convert the anhydrous sodium sulfate into sodium sulfate decahydrate slurry;
putting the sodium sulfate decahydrate slurry into a first settling separator for separating and settling sodium sulfate decahydrate and liquid, settling sodium sulfate decahydrate crystals at the bottom of the first settling separator due to high density, and floating water and oxygen-containing organic matters on the upper part of the first settling separator due to light density;
the sodium sulfate decahydrate crystal settled in the first settling separator carries part of liquid to be sent to a primary liquid-solid separator for separation, the separated solid is sent to a sodium sulfate decahydrate dehydration reaction knockout drum, and the separated water and oxygen-containing organic matters are sent to a sodium sulfate secondary hydration reactor; the water and the oxygen-containing organic matters floating in the first settling separator are sent to a sodium sulfate secondary hydration reactor;
adding anhydrous sodium sulfate into a secondary hydration reactor to hydrate and convert the anhydrous sodium sulfate into sodium sulfate decahydrate slurry;
placing the sodium sulfate decahydrate slurry in the secondary hydration reactor into a secondary liquid-solid separator for separation, sending the separated solid into a sodium sulfate primary hydration reactor, sending the separated liquid, namely a crude oxygen-containing organic matter, wherein the water content of the crude oxygen-containing organic matter is less than 5%, and sending the crude product into a crude product storage tank for storage;
in a sodium sulfate decahydrate dehydration reaction knockout drum, mixing a solid from a primary liquid-solid separator and sodium sulfate supersaturated slurry concentrated by a vacuum membrane distillation tower, dehydrating sodium sulfate decahydrate to generate anhydrous sodium sulfate and a saturated sodium sulfate solution, sending the anhydrous sodium sulfate and the saturated sodium sulfate solution into a second settling separator for settling, settling the anhydrous sodium sulfate to the bottom of the second settling separator with high density, and floating the saturated sodium sulfate solution on the upper part of the second settling separator with low density;
anhydrous sodium sulfate is discharged from the bottom of the second settling separator to a three-stage solid-liquid separator, liquid separated by the three-stage solid-liquid separator and liquid discharged from the upper part of the second settling separator are sent to a heat exchanger together, and solid separated by the three-stage solid-liquid separator returns to a sodium sulfate first-stage hydration reactor for recycling;
the liquid is heated by a heat exchanger and then sent to a vacuum membrane distillation tower, the concentration of sodium sulfate slurry at the outlet of the vacuum membrane distillation tower is controlled to be 43-45 percent and is sent to a sodium sulfate decahydrate dehydration reaction dehydration tank to be mixed with sodium sulfate decahydrate crystals for dehydration, water vapor evaporated by the vacuum membrane distillation tower is condensed by a condensing tower to obtain byproduct water, the byproduct water is sent to a product water storage tank for storage, and non-condensable gas at the top of the condensing tower is discharged by a vacuum pump.
Preferably, a heat exchange coil is arranged in the sodium sulfate primary hydration reactor, the reaction temperature in the sodium sulfate primary hydration reactor is maintained at 16-18 ℃, and the reaction time is 10-30 minutes under the stirring condition. Preferably, a heat exchange coil is arranged in the sodium sulfate secondary hydration reactor, the temperature in the sodium sulfate secondary hydration reactor is maintained at 16-18 ℃, and the reaction time is 10-30 minutes under the stirring condition. The hydration process of the anhydrous sodium sulfate is exothermic reaction, the lower the temperature is, the quicker the hydration reaction is, considering that the oxygen-containing organic matter with the highest freezing point in reaction water is acetic acid, the freezing point of the oxygen-containing organic matter is 16.7 ℃, so in order to prevent the acetic acid from being frozen out, the hydration reaction temperature is selected to be 16-18 ℃. Most natural gas and coal resources in China are distributed in northwest plateau areas, the areas are the first choice for building synthetic oil enterprises due to convenient raw material supply, plants are built in the areas with the average temperature not exceeding 15 ℃ in the years, refrigeration equipment does not need to be invested and built, the hydration reaction temperature can be maintained at about 17 ℃ by using a water-cooling heat exchanger under the local natural conditions, and the energy consumption is low.
In the scheme, the mass ratio of the addition amount of the anhydrous sodium sulfate in the sodium sulfate primary hydration reactor to the water in the reaction water is 60: 100. In the scheme, the mass ratio of the addition amount of the anhydrous sodium sulfate in the sodium sulfate secondary hydration reactor to the water in the reaction water is 20: 100. The anhydrous sodium sulfate is selected to be matched with the above components, so that water and oxygen-containing organic matters can be well matched and separated, and the treatment capacity of the anhydrous sodium sulfate is not increased to cause waste.
Preferably, the sedimentation process in the first sedimentation separator is carried out at 16-18 ℃.
Preferably, the heat exchanger heats the liquid to 60 ℃ and sends the liquid to the vacuum membrane distillation tower, the distillation temperature in the vacuum membrane distillation tower is controlled to be 50-60 ℃, and the vacuum degree is controlled to be 80-100 KPa.
For the separation principle of the present invention, some dilute aqueous solutions may also be used to separate water and some oxygenated organics using freeze crystallization, provided that the product of freeze crystallization of the aqueous solution does not contain the solute in the original solution. The F-T synthesis reaction water contains a certain amount of acetic acid and formic acid, the freezing points of the acetic acid and the formic acid are both higher than 0 ℃, if the F-T synthesis reaction water is frozen to be below 0 ℃, the formic acid and the acetic acid are also coagulated and separated out together with the water, and the aim of separating the organic acid from the water cannot be achieved. In addition, the freezing crystallization is often carried out at 0 ℃ or lower, which is an excessive energy consumption. Dilute aqueous solutions can also separate water by way of hydrate formation. The formation of hydrates does not require the reaction water to be chilled below 0 c, and therefore this separation process has significant energy advantages. Many inorganic salt compounds can absorb water or water vapor in the environment to form compounds with n (n ═ 1, 2, 3, 4 … …) crystal waters, the number of water molecules of each molecule of the crystal hydrates is the same, the composition of the molecules is fixed, and the molecules and water have strong interaction and can be regarded as new molecules. The invention combines solid-phase inorganic salt with water in F-T synthesis reaction water at a lower temperature to generate a crystalline hydrate with stable property, and separates water and oxygen-containing organic matters. Considering that the reaction water contains various oxygen-containing organic substances, the solid-phase inorganic salt must not react with or be soluble in the oxygen-containing organic substances (mainly organic acids) in the reaction water. After studying the physical and chemical properties of a plurality of inorganic salts, the inorganic salt sodium sulfate is found to be consistent with the formation of sodium sulfate decahydrate crystals by combining with water at low temperature, and organic acids, alcohols, aldehydes and ketones in reaction water do not react chemically and are not dissolved in oxygen-containing organic substances. The inorganic salt anhydrous sodium sulfate is produced in salt lake rich in brine, coexists with mirabilite, glauberite, epsomite, astrakanite, gypsum, glauberite, halite, natron and the like, and can also be generated by dehydrating mirabilite decahydrate, and the salt lake is low in price and rich in resources. Sodium sulfate is chemically stable, insoluble in ethanol, soluble in glycerin (glycerol) and water, and capable of absorbing water contained in air to be dissolved (deliquesced) even when exposed to air. The solubility of sodium sulfate in water is small at low temperatures (solubility at 0 ℃ C. is 4.9 grams sodium sulfate per 100 grams water) and increases with increasing temperature. The solubility of sodium sulphate reached a maximum at 40 c, 48.8 per 100 g of water. The temperature continues to rise and the solubility slowly decreases instead. The phase transition point of the anhydrous sodium sulfate and the sodium sulfate decahydrate is 32.4 ℃ (melting point temperature), and when the solution temperature is higher than 32.4 ℃, the precipitated solid is the anhydrous sodium sulfate; when the temperature is less than 32.4 ℃, the solid separated out is sodium sulfate decahydrate crystals. The anhydrous sodium sulfate and sodium sulfate decahydrate crystals can be mutually converted at a phase transition point of 32.4 ℃, and are shown as the following formula:
the anhydrous sodium sulfate and water are combined to generate sodium sulfate decahydrate, which is a complex phase change process, and the process comprises the processes of crystallization precipitation of sodium sulfate decahydrate, gradient change of solution concentration and the like besides releasing 77.06kJ/mol of phase change latent heat. Adding anhydrous sodium sulfate into F-T synthetic reaction water at a temperature lower than 32.4 ℃ (melting point temperature), dissolving sodium sulfate firstly to form a saturated sodium sulfate solution, continuously adding anhydrous sodium sulfate into the saturated solution, combining sodium sulfate entering a system with water in the solution to generate sodium sulfate decahydrate crystals, causing the saturated solution to be further supersaturated due to solidification of water consumed for generating the sodium sulfate decahydrate crystals by combining with the anhydrous sodium sulfate, thereby precipitating more sodium sulfate decahydrate crystals, reducing the amount of sodium sulfate in the solution along with the crystallization of the sodium sulfate decahydrate, stopping the precipitation of the sodium sulfate decahydrate crystals when the addition of the anhydrous sodium sulfate solids is stopped and the sodium sulfate content in the solution is reduced to a saturated value, balancing the dissolution and precipitation, maintaining the saturated state, continuously adding the anhydrous sodium sulfate solids, continuing the hydration reaction, and when the amount of the added anhydrous sodium sulfate reaches 78.89 g per 100 g of sodium sulfate in water, all water components in the F-T synthesis reaction water are combined with sodium sulfate to generate relatively stable sodium sulfate decahydrate crystals, and the crystals are centrifugally separated, so that the separation of the F-T synthesis reaction water and the oxygen-containing organic matters can be completed. Thus, the present invention employs anhydrous sodium sulfate as the separation medium.
Compared with the prior art, the invention has the advantages that: the invention utilizes the property that anhydrous sodium sulfate is hydrated to generate stable crystalline hydrate, concentrates the organic matters in the F-T synthesis reaction water until the water content is less than 5 percent, reduces the material handling capacity of the organic matter recovery procedure in the subsequent working section by 85 to 90 percent, enables the separation method which can not be used due to overlarge energy consumption to be feasible, and greatly reduces the separation cost and the equipment investment; anhydrous sodium sulfate is dehydrated and converted into inorganic salt without crystal water at a lower temperature, and the inorganic salt is filtered and separated from the solution, so that the separated anhydrous salt is recycled, the concentration cost is reduced, and the economic benefit of an enterprise is improved; the water generated by the F-T synthesis reaction is recovered by utilizing the vacuum membrane distillation technology, so that the problem of serious unbalance of water balance of synthetic oil enterprises can be solved.
Drawings
FIG. 1 is a schematic diagram of a process flow structure according to an embodiment of the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
As shown in fig. 1, the apparatus for recovering organic substances from the water of the ft-synthesis reaction in this example comprises:
the system comprises a sodium sulfate primary hydration reactor 1, wherein a heat exchange coil and a stirrer are arranged in the sodium sulfate primary hydration reactor 1, the upper part of the sodium sulfate primary hydration reactor 1 is provided with a first inlet for inputting F-T synthetic reaction water, the top part of the sodium sulfate primary hydration reactor 1 is provided with a second inlet for adding anhydrous sodium sulfate, and the bottom part of the sodium sulfate primary hydration reactor is provided with an outlet for discharging sodium sulfate decahydrate slurry;
the top of the first sedimentation separator 2 is provided with an input port communicated with the outlet of the sodium sulfate primary hydration reactor 1, the bottom of the first sedimentation separator 2 is provided with a first outlet for outputting sodium sulfate decahydrate crystals, and the upper part of the first sedimentation separator 2 is also provided with a second outlet;
a first-stage solid-liquid separator 3, the top of which is provided with an inlet communicated with the first outlet of the first settling separator 2, the bottom of which is provided with a first outlet for outputting separated solids, and the lower part of which is provided with a second outlet;
the sodium sulfate decahydrate dehydration reaction stripping tank 4 is provided with a first inlet communicated with the first outlet of the primary solid-liquid separator 3 and a second inlet independent of the first inlet at the top, a heat exchange coil and a stirrer are arranged in the sodium sulfate decahydrate dehydration reaction stripping tank 4, and an output port is arranged at the bottom;
a sodium sulfate secondary hydration reactor 5, the top of which is provided with a first inlet for adding anhydrous sodium sulfate, the upper part of which is provided with a second inlet communicated with the second outlet of the first sedimentation separator 2 and the second outlet of the primary solid-liquid separator 3, and the bottom of which is provided with an outlet for discharging sodium sulfate decahydrate slurry; a heat exchange coil and a stirrer are arranged in the sodium sulfate secondary hydration reactor 5;
a secondary solid-liquid separator 6, the top of which is provided with an inlet communicated with the outlet of the sodium sulfate secondary hydration reactor 5, the bottom of which is provided with a first outlet communicated with the second inlet of the sodium sulfate primary hydration reactor 1, and the lower part of the secondary solid-liquid separator 6 is provided with a second outlet for outputting crude oxygen-containing organic matters;
a crude product storage tank 7 for storing crude oxygen-containing organic matter, which is communicated with a second outlet of the secondary solid-liquid separator 6;
a second sedimentation separator 8 having an inlet at the top communicating with the outlet of the sodium sulfate decahydrate dehydration reaction tank 4, a first outlet at the bottom and a second outlet at the upper part;
a three-stage solid-liquid separator 9, the top of which is provided with an inlet communicated with the first outlet of the second settling separator 8, the bottom of which is provided with a first outlet communicated with the second inlet of the sodium sulfate first-stage hydration reactor 1, and the lower part of which is provided with a second outlet;
the heat exchanger 10 is provided with an inlet communicated with the second outlet of the second settling separator 8 and the second outlet of the three-stage solid-liquid separator 9 and an output port for outputting the liquid after heat exchange;
a vacuum membrane distillation tower 11, the top of which is provided with an inlet communicated with the output port of the heat exchanger 10, the bottom of which is provided with a first outlet communicated with the second inlet of the sodium sulfate decahydrate dehydration reaction tank 4, and the lower part of which is provided with a second outlet; and
a condensing tower 12 having an inlet in the middle communicating with the second outlet of the vacuum membrane distillation tower 11, a first outlet in the top communicating with a vacuum pump 13, and a second outlet in the bottom communicating with a product water storage tank 14.
The method for recovering the organic matters in the F-T synthesis reaction water comprises the following steps:
feeding reaction water from the F-T synthetic wastewater filter into a sodium sulfate primary hydration reactor 1, adding anhydrous sodium sulfate into the primary hydration reactor 1, wherein the mass ratio of the addition amount of the anhydrous sodium sulfate to water in the reaction water is 60:100, maintaining the reaction temperature in the sodium sulfate primary hydration reactor 1 at 16-18 ℃, and reacting for 10-30 minutes under the stirring condition to convert the anhydrous sodium sulfate into sodium sulfate decahydrate slurry;
placing the sodium sulfate decahydrate slurry into a first settling separator 2 for separating and settling sodium sulfate decahydrate and liquid, wherein the settling process in the first settling separator 2 is maintained at 16-18 ℃, sodium sulfate decahydrate crystals settle at the bottom of the first settling separator 2 due to high density, and water and oxygen-containing organic matters float at the upper part of the first settling separator 2 due to light density;
the sodium sulfate decahydrate crystal settled in the first settling separator 2 carries part of liquid to be sent to a primary liquid-solid separator 3 for separation, the separated solid is sent to a sodium sulfate decahydrate dehydration reaction tank 4, and the separated water and oxygen-containing organic matters are sent to a sodium sulfate secondary hydration reactor 5; the water and the oxygen-containing organic matters floating in the first settling separator 2 are sent to a sodium sulfate secondary hydration reactor 5;
adding anhydrous sodium sulfate into a secondary hydration reactor 5, wherein the mass ratio of the added amount of the anhydrous sodium sulfate to water in reaction water is 20:100, maintaining the temperature in the sodium sulfate secondary hydration reactor 5 at 16-18 ℃, and reacting for 10-30 minutes under the stirring condition, so that the anhydrous sodium sulfate is hydrated and converted into sodium sulfate decahydrate slurry;
the sodium sulfate decahydrate slurry in the secondary hydration reactor 5 is put into a secondary liquid-solid separator 6 for separation, the separated solid is sent into a sodium sulfate primary hydration reactor 1, the separated liquid is a crude oxygen-containing organic matter, the water content of the crude oxygen-containing organic matter is less than 5 percent, and the crude oxygen-containing organic matter is sent into a crude product storage tank 7 for storage;
in a sodium sulfate decahydrate dehydration reaction tank 4, mixing the solid from the primary liquid-solid separator 3 and the concentrated sodium sulfate supersaturated slurry from the vacuum membrane distillation tower 11, dehydrating sodium sulfate decahydrate to generate anhydrous sodium sulfate and a saturated sodium sulfate solution, sending the anhydrous sodium sulfate and the saturated sodium sulfate solution into a second settling separator 8 for settling, wherein the anhydrous sodium sulfate is precipitated to the bottom of the second settling separator 8 in a high density, and the saturated sodium sulfate solution is floated on the upper part of the second settling separator 8 in a low density;
anhydrous sodium sulfate is discharged from the bottom of the second settling separator 8 to a three-stage solid-liquid separator 9, liquid separated by the three-stage solid-liquid separator 9 and liquid discharged from the upper part of the second settling separator 8 are sent to a heat exchanger 10 together, and solid separated by the three-stage solid-liquid separator 9 returns to the sodium sulfate first-stage hydration reactor 1 for recycling;
the liquid is heated to 60 ℃ by the heat exchanger 10 and then sent to the vacuum membrane distillation tower 11, the distillation temperature in the vacuum membrane distillation tower 11 is controlled to be 50-60 ℃, the vacuum degree is controlled to be 80-100 KPa, the concentration of sodium sulfate slurry at the outlet of the vacuum membrane distillation tower 11 is controlled to be 44.1%, the sodium sulfate slurry is sent to the sodium sulfate decahydrate dehydration reaction tank 4 to be mixed and dehydrated with sodium sulfate decahydrate crystals, water vapor evaporated by the vacuum membrane distillation tower 11 is condensed by the condensation tower 12 to obtain byproduct water, the byproduct water is sent to the product water storage tank 14 to be stored, and non-condensable gas at the top of the condensation tower 12 is discharged by the vacuum pump 13.
Claims (7)
1. A method for recovering organic matters in F-T synthesis reaction water is characterized by comprising the following steps: comprises the following steps
Feeding reaction water from the F-T synthetic wastewater filter into a sodium sulfate primary hydration reactor, and adding anhydrous sodium sulfate into the primary hydration reactor to hydrate the anhydrous sodium sulfate and convert the anhydrous sodium sulfate into sodium sulfate decahydrate slurry;
putting the sodium sulfate decahydrate slurry into a first settling separator for separating and settling sodium sulfate decahydrate and liquid, settling sodium sulfate decahydrate crystals at the bottom of the first settling separator due to high density, and floating water and oxygen-containing organic matters on the upper part of the first settling separator due to light density;
the sodium sulfate decahydrate crystal settled in the first settling separator carries part of liquid to be sent to a primary liquid-solid separator for separation, the separated solid is sent to a sodium sulfate decahydrate dehydration reaction tank, and the separated water and oxygen-containing organic matters are sent to a sodium sulfate secondary hydration reactor; the water and the oxygen-containing organic matters floating in the first settling separator are sent to a sodium sulfate secondary hydration reactor;
adding anhydrous sodium sulfate into a secondary hydration reactor to hydrate and convert the anhydrous sodium sulfate into sodium sulfate decahydrate slurry;
placing the sodium sulfate decahydrate slurry in the secondary hydration reactor into a secondary liquid-solid separator for separation, sending the separated solid into a sodium sulfate primary hydration reactor, sending the separated liquid, namely a crude oxygen-containing organic matter, wherein the water content of the crude oxygen-containing organic matter is less than 5%, and sending the crude product into a crude product storage tank for storage;
in a sodium sulfate decahydrate dehydration reaction knockout drum, mixing a solid from a primary liquid-solid separator and sodium sulfate supersaturated slurry concentrated by a vacuum membrane distillation tower, dehydrating sodium sulfate decahydrate to generate anhydrous sodium sulfate and a saturated sodium sulfate solution, sending the anhydrous sodium sulfate and the saturated sodium sulfate solution into a second settling separator for settling, settling the anhydrous sodium sulfate to the bottom of the second settling separator with high density, and floating the saturated sodium sulfate solution on the upper part of the second settling separator with low density;
anhydrous sodium sulfate is discharged from the bottom of the second settling separator to a three-stage solid-liquid separator, liquid separated by the three-stage solid-liquid separator and liquid discharged from the upper part of the second settling separator are sent to a heat exchanger together, and solid separated by the three-stage solid-liquid separator returns to a sodium sulfate first-stage hydration reactor for recycling;
the liquid is heated by a heat exchanger and then sent to a vacuum membrane distillation tower, the concentration of sodium sulfate slurry at the outlet of the vacuum membrane distillation tower is controlled to be 43-45 percent and is sent to a sodium sulfate decahydrate dehydration reaction dehydration tank to be mixed with sodium sulfate decahydrate crystals for dehydration, water vapor evaporated by the vacuum membrane distillation tower is condensed by a condensing tower to obtain byproduct water, the byproduct water is sent to a product water storage tank for storage, and non-condensable gas at the top of the condensing tower is discharged by a vacuum pump.
2. The method for recovering organics in fischer-tropsch synthesis reaction water as claimed in claim 1, wherein: the heat exchange coil is arranged in the sodium sulfate primary hydration reactor, the reaction temperature in the sodium sulfate primary hydration reactor is maintained at 16-18 ℃, and the reaction time is 10-30 minutes under the stirring condition.
3. The method for recovering organics in fischer-tropsch synthesis reaction water as claimed in claim 2, wherein: the mass ratio of the addition amount of the anhydrous sodium sulfate in the sodium sulfate primary hydration reactor to the water in the reaction water is 60: 100.
4. The method for recovering organics in fischer-tropsch synthesis reaction water as claimed in claim 1, wherein: the sedimentation process in the first sedimentation separator is carried out at 16-18 ℃.
5. The method for recovering organics in fischer-tropsch synthesis reaction water as claimed in claim 1, wherein: a heat exchange coil is arranged in the sodium sulfate secondary hydration reactor, the temperature in the sodium sulfate secondary hydration reactor is maintained at 16-18 ℃, and the reaction time is 10-30 minutes under the stirring condition.
6. The method for recovering organics in fischer-tropsch synthesis reaction water as claimed in claim 5, wherein: the mass ratio of the addition amount of the anhydrous sodium sulfate in the sodium sulfate secondary hydration reactor to the water in the reaction water is 20: 100.
7. The method for recovering organic matters in F-T synthesis reaction water according to any one of claims 1 to 6, which is characterized in that: the heat exchanger heats the liquid to 60 ℃ and sends the liquid to the vacuum membrane distillation tower, the distillation temperature in the vacuum membrane distillation tower is controlled to be 50-60 ℃, and the vacuum degree is controlled to be 80-100 KPa.
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