CN104150670A - Processing device and method for Fischer-Tropsch synthetic water - Google Patents
Processing device and method for Fischer-Tropsch synthetic water Download PDFInfo
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- CN104150670A CN104150670A CN201410438559.2A CN201410438559A CN104150670A CN 104150670 A CN104150670 A CN 104150670A CN 201410438559 A CN201410438559 A CN 201410438559A CN 104150670 A CN104150670 A CN 104150670A
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Abstract
The invention discloses a processing device and method for Fischer-Tropsch synthetic water. The processing device comprises a dealcoholization system (1) and an extraction system (2); the dealcoholization system (1) is used for removing light alcohol and heavy alcohol from the Fischer-Tropsch synthetic water; the extraction system (2) is connected with the dealcoholization system (1) by a dealcoholization water pipeline and is used for extracting organic acid from dealcoholized water in the dealcoholization system (1). According to the invention, by arranging the dealcoholization system (1) and the extraction system (2) in the processing device, the dealcoholization system (1) is utilized to remove the light alcohol and the heavy alcohol in the Fischer-Tropsch synthetic water and then the extraction system (2)is utilized to extract the organic acid in the dealcoholized water obtained after the light alcohol and the heavy alcohol are removed; effective separation of organisms in the Fischer-Tropsch synthetic water can be implemented by adopting the simple processing device; moreover, recycling efficiency of the organisms in the Fischer-Tropsch synthetic water is improved and economic benefits are increased; and meanwhile, the processing device can improve the purification degree of the Fischer-Tropsch synthetic water and create the advantage for recycling the Fischer-Tropsch synthetic water.
Description
Technical field
The present invention relates to waste water treatment process technical field, in particular to a kind for the treatment of unit and treatment process of utilizing Fischer-Tropsch synthetic water.
Background technology
Along with the world limited day by day exhaustion of petroleum resources and the continuous enhancing to environmental protection consciousness, research becomes one of direction of world-technology exploitation with the substitute of finding eco-friendly petroleum-based energy.Mineral substance, coal and conversion of natural gas technology are one of important channels of diversification solution petroleum resources shortage problem, have become experts and scholars' common recognition.Coal and Sweet natural gas synthesize (Fischer-Tropsch Synthesis, F-T) reaction by Fischer-Tropsch, are converted into oil or other Chemicals, can solve petroleum resources shortage on the one hand, meet the demand of national economy rapid growth to the energy; Can produce on the other hand more useful Chemicals, drive the development of local economy, also can reduce the environmental pollution that direct burning causes simultaneously, significant.
The technology such as ICL for Indirect Coal Liquefaction technology is taking coal as raw material,, oil product upgrading processing synthetic by gasification, Fischer-Tropsch obtain the low-carbon (LC) clean conversion technology of motor fluid fuel oil and chemicals, are also one of directions of utilizing of coal in China clean conversion.
Fischer-Tropsch wherein can produce the synthetic water with the similar equivalent of oil product when synthesizing production liquid fuel.According to the indirect liquefying plant actual operating state of domestic several covers, 1 ton of oil of the every production of ICL for Indirect Coal Liquefaction production equipment, produce the Fischer-Tropsch synthetic water of 1.2 tons of left and right; The organic oxygen-containing compound that approximately contains 10wt% in Fischer-Tropsch synthetic water, is mainly alcohol, ketone and carboxylic acid, wants these separating organic matters contained in water out, needs to adopt multiple separation means, needs altogether tens towers.Because domestic Fischer-Tropsch synthesizer project scale is less, want oxygenatedchemicals in Fischer-Tropsch synthetic water to reclaim comprehensively, cost is too high, uneconomical; Current domestic Fischer-Tropsch synthesizer synthetic water process all adopt Simple process, existing process program have distillation and washing combination process and distillation and in and combination process.
As can be seen here, at present organism recovery process complexity in Fischer-Tropsch synthetic water, cost is high and efficiency is low, therefore needs a kind of low cost of exploitation and the simple organism recovery process of technique badly.
Summary of the invention
The present invention aims to provide a kind for the treatment of unit and treatment process of Fischer-Tropsch synthetic water, to simplify the processing of Fischer-Tropsch synthetic water.
To achieve these goals, according to an aspect of the present invention, provide a kind for the treatment of unit of Fischer-Tropsch synthetic water, this treatment unit comprises: dealcoholysis system and extracting system; Dealcoholysis system is in order to remove light alcohols and the heavy alcohol in Fischer-Tropsch synthetic water; Extracting system is connected by dealcoholysis water pipeline with dealcoholysis system, in order to extract from the organic acid in the dealcoholysis water of dealcoholysis system.
Further, above-mentioned extracting system comprises that organic acid extraction tower, in order to extract the organic acid in dealcoholysis water, is connected by dealcoholysis water pipeline with dealcoholysis system.
Further, above-mentioned extracting system also comprises that extraction agent recovery unit is to reclaim extraction agent, between extraction agent recovery unit and organic acid extraction tower, be provided with extraction liquid pipeline, extraction liquid pipeline is delivered to extraction agent recovery unit in order to will extract organic acid extraction liquid.
Further, between above-mentioned organic acid extraction tower and extraction agent recovery unit, be also provided with extraction agent pipeline, the extraction agent of recovery is transmitted back to organic acid extraction tower by extraction agent pipeline.
Further, above-mentioned extracting system also comprises extraction wastewater sedimentation unit, and in order to the water in extraction wastewater is separated with extraction agent, extraction wastewater sedimentation unit is connected by extraction wastewater pipeline with organic acid extraction tower.
Further, between above-mentioned extraction wastewater sedimentation unit and organic acid extraction tower, be provided with containing extraction waste line extraction wastewater sedimentation unit is obtained to be transmitted back to organic acid extraction tower containing extraction waste water.
Further, above-mentioned dealcoholysis system comprises dealcoholysis unit, between dealcoholysis unit and extracting system, is connected by dealcoholysis water pipeline.
Further, above-mentioned dealcoholysis unit comprises: dealcoholize column and water wash column, be provided with dealcoholysis water pipeline between dealcoholize column and extracting system; Water wash column is in order to the heavy alcohol isolate from dealcoholize column is washed, and between dealcoholize column, is provided with heavy alcohol pipeline.
Further, above-mentioned dealcoholysis system also comprises that heat exchange unit is in order to Fischer-Tropsch synthetic water is carried out to preheating, and between dealcoholize column, is provided with synthetic water pipeline.
Further, between above-mentioned dealcoholize column and heat exchange unit, be provided with the hot steam of hot steam pipeline in order to carry dealcoholize column to produce to heat exchange unit.
Further, between above-mentioned water wash column and heat exchange unit, also arrange by washing water recovery line and be delivered to heat exchange unit in order to the washing water that water wash column is produced.
According to a further aspect in the invention, provide a kind for the treatment of process of Fischer-Tropsch synthetic water, this treatment process comprises: step S1, Fischer-Tropsch synthetic water is carried out to dealcoholation treatment, obtain dealcoholysis water, light alcohols isolate and heavy alcohol isolate; Step S2, dealcoholysis water is extracted, obtain depickling water and organic acid isolate.
Further, in step S2, the extraction agent that extraction adopts is selected from one or more in the group of tributyl phosphate, ethyl acetate and trioctylamine composition.
Further, in step S2, the temperature of extraction is 30～40 DEG C; Pressure is 0.3～0.8MPa.
Further, after step S2, treatment process also comprises: organic acid isolate is carried out to extraction agent recycling, obtain organic acid and extraction agent; Extraction agent is returned to step S2.
Further, after step S2, treatment process also comprises: depickling waste water is carried out to sedimentation processing, obtain containing extraction waste water with without extraction waste water; To return to step S2 containing extraction waste water.
Further, before step S1, treatment process also comprises carries out pre-warmed step to Fischer-Tropsch synthetic water, preferably Fischer-Tropsch synthetic water is preheated to 70～95 DEG C.
Further, the dealcoholation treatment in above-mentioned steps S1 adopts the mode of distillation to carry out, and preferably the temperature of distillation is 110～150 DEG C, and pressure is 0.1～0.35MPa, preferably 0.2MPa.
Further, above-mentioned treatment process also comprises heavy alcohol isolate is washed to the process that obtains heavy alcohol.
Further, the process of above-mentioned washing comprises: heavy alcohol isolate is cooled to 35～45 DEG C; Heavy alcohol isolate after cooling is washed, obtained heavy alcohol and water wash water; Washing water is returned to step S1.
Apply treatment unit and the treatment process of a kind of Fischer-Tropsch synthetic water of technical scheme of the present invention, by dealcoholysis system and extracting system are set in treatment unit, utilize dealcoholysis system that the light alcohols in Fischer-Tropsch synthetic water and heavy alcohol are removed, then utilize extracting system to extract the organic acid removing in light alcohols and heavy alcohol dealcoholysis water afterwards, adopt simple treatment unit can realize organic effective separation in Fischer-Tropsch synthetic water, and improved organic recycling efficiency in Fischer-Tropsch synthetic water, increase economic benefit; Meanwhile, above-mentioned treatment unit can improve the degree of purification of Fischer-Tropsch synthetic water, for its recycling creates favorable conditions.
Brief description of the drawings
The Figure of description that forms the application's a part is used to provide a further understanding of the present invention, and schematic description and description of the present invention is used for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows the processing technological flow figure of the Fischer-Tropsch synthetic water of a kind of exemplary embodiments according to the present invention.
Embodiment
It should be noted that, in the situation that not conflicting, the feature in embodiment and embodiment in the application can combine mutually.Describe below with reference to the accompanying drawings and in conjunction with the embodiments the present invention in detail.
In order to realize above-mentioned purpose of the present invention, in a kind of typical embodiment of the present invention, a kind for the treatment of unit of Fischer-Tropsch synthetic water is provided, and above-mentioned treatment unit comprises dealcoholysis system 1 and extracting system 2, and dealcoholysis system 1 is in order to remove light alcohols and the heavy alcohol in Fischer-Tropsch synthetic water; Extracting system 2 is connected by dealcoholysis water pipeline with dealcoholysis system 1, in order to extract from the organic acid in the dealcoholysis water of dealcoholysis system 1.
Above-mentioned treatment unit of the present invention, by dealcoholysis system 1 and extracting system 2 are set in treatment unit, utilize dealcoholysis system 1 that the light alcohols in Fischer-Tropsch synthetic water and heavy alcohol are removed, then utilize extracting system 2 to extract the organic acid removing in light alcohols and heavy alcohol dealcoholysis water afterwards, adopt simple treatment unit can realize organic effective separation in Fischer-Tropsch synthetic water, and improved organic recycling efficiency in Fischer-Tropsch synthetic water, increase economic benefit; Meanwhile, above-mentioned treatment unit can improve the degree of purification of Fischer-Tropsch synthetic water, for its recycling creates favorable conditions.
According to the extracting system 2 in above-mentioned treatment unit of the present invention, those skilled in the art can improve existing extraction plant, as long as can realize, the organic acid in dealcoholysis water are carried out to extracting and separating, such as mixing tank, water separator combination.In a kind of preferred embodiment of the present invention, above-mentioned extracting system 2 comprises that organic acid extraction tower 3 is in order to extract the organic acid in above-mentioned dealcoholysis water, and this organic acid extraction tower 3 is connected by dealcoholysis water pipeline with above-mentioned dealcoholysis system 1.Utilize above-mentioned dealcoholysis water pipeline to send into the organic acid extraction tower 3 of extracting system 2 containing organic acid dealcoholysis water by removing after light alcohols and heavy alcohol, in organic acid extraction tower 3, utilize extraction agent to extract organic acid, realize and remove organic acid object.Therefore, the organic acid in Fischer-Tropsch synthetic water is reclaimed in arranging separately of organic acid extraction tower 3 of the present invention, is convenient to it and further utilizes, and further purified synthetic water after treatment.
In order to reduce the cost and the utilising efficiency that improves extraction agent of extraction agent, above-mentioned extracting system 2 of the present invention can also arrange extraction agent recovery unit 4, in order to reclaim extraction agent.Meanwhile, between extraction agent recovery unit 4 and above-mentioned organic acid extraction tower 3, extraction liquid pipeline is set, is delivered to extraction agent recovery unit 4 by above-mentioned extraction liquid pipeline by extracting organic acid extraction liquid in organic acid extraction tower 3.Above-mentioned extraction agent recovery unit 4, by carrying out extraction agent recovery to containing organic acid extraction liquid, has both been realized the recovery of extraction agent, has improved again the organic acid rate of recovery, and the organic acid of recovery can sell, and reduces enterprise's production cost; Or enter hydrotreater, for the production of liquefied gas and petroleum naphtha and fuel gas.
Based on above-mentioned same cost consideration, in a kind of preferred embodiment of the present invention, between above-mentioned organic acid extraction tower 3 and above-mentioned extraction agent recovery unit 4, be also provided with extraction agent pipeline, this extraction agent pipeline is transmitted back in organic acid extraction tower 3 in order to the extraction agent that extraction agent recovery unit 4 is reclaimed, and then realizes the recycling of extraction agent.
In the extraction wastewater after above-mentioned organic acid extraction tower 3 extractions, may contain extraction agent, in order further to reclaim extraction agent, in the another kind of preferred embodiment of the present invention, above-mentioned extracting system 2 also comprises extraction wastewater sedimentation unit 5, in order to the water in extraction wastewater is separated with extraction agent, above-mentioned extraction wastewater sedimentation unit 5 is connected by extraction wastewater pipeline with above-mentioned organic acid extraction tower 3.Extraction wastewater, by after standing sedimentation, just do not realized layering containing the waste water of extraction agent with containing between the waste water of extraction agent in extraction wastewater sedimentation unit 5, is conducive to recycling containing the extraction agent in the waste water of extraction agent.
For the extraction agent containing in the waste water of extraction agent in above-described embodiment is rationally utilized, between the above-mentioned extraction wastewater sedimentation unit 5 of the present invention and above-mentioned organic acid extraction tower 3, further arrange containing extraction waste line, to realize, above-mentioned extraction wastewater sedimentation unit 5 is obtained being transmitted back in above-mentioned organic acid extraction tower 3 containing extraction waste water, carry out organic acid extraction by the dealcoholysis water in organic acid extraction tower 3, realize the further recycling of extraction agent.
In above-mentioned treatment unit of the present invention, dealcoholysis system 1 is for removing light alcohols and the heavy alcohol in Fischer-Tropsch synthetic water, those skilled in the art can suitably adjust according to the set-up mode of existing dealcoholysis system 1, as long as can remove light alcohols and heavy alcohol from Fischer-Tropsch synthetic water.In a kind of preferred embodiment of the present invention, above-mentioned dealcoholysis system 1 comprises dealcoholysis unit 6, realizes removing of alcohol in Fischer-Tropsch synthetic water, and carries out dealcoholysis by dealcoholysis unit is set, and the alcohol of being convenient to removing is recycled.In addition, between above-mentioned dealcoholysis unit 6 and above-mentioned extracting system 2, be connected by above-mentioned dealcoholysis water pipeline, the dealcoholysis water after 6 dealcoholysis of dealcoholysis unit is flowed in extracting system 2 and is carried out follow-up organic acid extraction by dealcoholysis water pipeline.
As long as above-mentioned dealcoholysis unit 6 can be realized the alcohol in Fischer-Tropsch synthetic water to remove and be convenient to and recycle, as for the concrete set-up mode of above-mentioned dealcoholysis unit 6, the difference of the light alcohols that those skilled in the art can recycle as required or heavy alcohol, the dealcoholysis unit 6 that appropriate design is used, such as steam stripped tower.In a kind of preferred embodiment of the present invention, above-mentioned dealcoholysis unit 6 comprises dealcoholize column and water wash column 8, and dealcoholize column is connected with above-mentioned extracting system 2 by above-mentioned dealcoholysis water pipeline; Between water wash column 8 and above-mentioned dealcoholize column, be provided with heavy alcohol pipeline, in order to the heavy alcohol isolate from above-mentioned dealcoholize column is washed, in the above embodiment of the present invention, by dealcoholize column is set, the light alcohols in Fischer-Tropsch synthetic water is separated, then by heavy alcohol pipeline, heavy alcohol isolate is extracted out, and then both realized the separation of the alcohols to the different densities in Fischer-Tropsch synthetic water, also facilitate and follow-up organic acid is effectively extracted.Because heavy alcohol concentrates on the middle part of dealcoholize column after processing in dealcoholize column, the interface that therefore preferably heavy alcohol pipeline is connected with dealcoholize column is arranged on the middle part sidewall of dealcoholize column.Heavy alcohol isolate enters in water wash column 8 by heavy alcohol pipeline, makes carried secretly a small amount of light alcohols water-soluble by washing, thereby realizes and the separating of heavy alcohol.The set-up mode of above-mentioned dealcoholysis of the present invention unit 6 is convenient to light alcohols and heavy alcohol to recycle respectively, has improved utility value.
Above-mentioned dealcoholysis system 1 of the present invention can realize carries out dealcoholation treatment to Fischer-Tropsch synthetic water of the present invention, but in order further to reduce processing cost, shorten the dealcoholation treatment time, in a kind of preferred embodiment of the present invention, above-mentioned dealcoholysis system 1 also comprises that heat exchange unit 9 is in order to above-mentioned Fischer-Tropsch synthetic water is carried out to preheating, and is provided with synthetic water pipeline between above-mentioned dealcoholize column.By heat exchange unit 9 is set, can be heated in advance or approach the required temperature of dealcoholize column to entering the Fischer-Tropsch synthetic water of dealcoholize column, shorten the dealcoholation treatment time, and then shorten the Fischer-Tropsch synthetic water treatment process cycle, improve the processing efficiency for the treatment of unit.
In above-mentioned preferred embodiment, also there is a large amount of heats dealcoholysis unit 6 after dealcoholysis, in order further above-mentioned heat rationally to be utilized, can also between above-mentioned dealcoholize column and heat exchange unit 9, hot steam pipeline be set, in order to the hot steam of carrying above-mentioned dealcoholize column to produce to above-mentioned heat exchange unit 9, thereby the waste heat of realizing sharp dealcoholysis unit 6 preheats pending Fischer-Tropsch synthetic water, the energy that has both rationally utilized system to produce, has shortened again process cycle.
In addition,, after above-mentioned water wash column 8 is washed heavy alcohol isolate, the washing water that contains a small amount of light alcohols can also remove light alcohols wherein by again entering dealcoholysis system 1.Therefore,, in another preferred embodiment of the present invention, between above-mentioned water wash column 8 and above-mentioned heat exchange unit 9, also arrange by washing water recovery line and be delivered to above-mentioned heat exchange unit 9 in order to the washing water that above-mentioned water wash column 8 is produced.
In the another kind of typical embodiment of the present invention, a kind for the treatment of process of Fischer-Tropsch synthetic water is provided, this treatment process comprises: step S1, Fischer-Tropsch synthetic water is carried out to dealcoholation treatment, obtain dealcoholysis water, light alcohols isolate and heavy alcohol isolate; Step S2, dealcoholysis water is extracted, obtain depickling water and organic acid isolate.
Above-mentioned treatment process of the present invention, by Fischer-Tropsch synthetic water is first carried out to dealcoholation treatment, remove light alcohols isolate and heavy alcohol isolate in Fischer-Tropsch synthetic water, and then relatively pure dealcoholysis hydromining is separated by the method for extraction the organic acid removing in water, obtain removing organic acid water and organic acid isolate.This treatment process adopts Organic Alcohol and organic acid substep is removed, and has realized organic effective separation in Fischer-Tropsch synthetic water, and improved organic recycling efficiency in Fischer-Tropsch synthetic water by simple process, has increased economic benefit; Meanwhile, above-mentioned treatment process can improve the degree of purification of Fischer-Tropsch synthetic water, for the recycling of the Fischer-Tropsch synthetic wastewater after purifying creates favorable conditions.
In above-mentioned steps S2, those skilled in the art can be according to the performance of the source of extraction agent, price and extraction agent, selects applicable extraction agent to extract the organic acid in above-mentioned dealcoholysis water.In the preferred embodiment of the invention, the extraction agent that above-mentioned extraction adopts is selected from one or more in the group of trioctylamine, tributyl phosphate, ethyl acetate composition.
In above-mentioned steps S2, those skilled in the art can arrange suitable extraction temperature and extracting pressure according to the difference of selected extraction agent.In the present invention, the temperature of preferred above-mentioned extraction is 30～40 DEG C; Pressure be 0.3～0.8MPa in said temperature and pressure range, high to organic acid extraction efficiency.
In order to reduce the cost and the utilising efficiency that improves extraction agent of extraction agent, in a kind of preferred embodiment of the present invention, after above-mentioned steps S2, also comprise above-mentioned organic acid isolate is carried out to extraction agent recycling, obtain organic acid and extraction agent; And above-mentioned extraction agent is returned to the step of above-mentioned steps S2.In above-described embodiment, both improved the rate of recovery of extraction agent, and improved again the organic acid rate of recovery, the organic acid of recovery can sell, and reduces enterprise's production cost; Or enter hydrotreater and produce liquefied gas and petroleum naphtha and fuel gas.
In the extraction wastewater after above-mentioned organic acid extraction tower 3 extractions, may contain extraction agent, in order further to reclaim extraction agent, realize the maximization of extraction agent utilization ratio, in another preferred embodiment of the present invention, above-mentioned treatment process, after step S2, also comprises: above-mentioned depickling waste water is carried out to sedimentation processing, obtain containing extraction waste water with without extraction waste water; Return to above-mentioned steps S2 by above-mentioned containing extraction waste water.Extraction wastewater, by after standing sedimentation, just do not realized layering containing the waste water of extraction agent with containing between the waste water of extraction agent in extraction wastewater sedimentation unit 5, is conducive to recycling containing the extraction agent in the waste water of extraction agent.Meanwhile, remove extraction agent without extraction waste water because degree of purification is higher, the water can be used as in water-washing step is washed heavy alcohol isolate, also can be for the water distribution of gasification coal water slurry or decontaminated water treatment system.
Above-mentioned treatment process of the present invention can realize carries out dealcoholation treatment to the light alcohols in Fischer-Tropsch synthetic water of the present invention and heavy alcohol, but in order further to reduce processing cost, shorten the dealcoholation treatment time, in a kind of preferred embodiment of the present invention, before above-mentioned steps S1, also comprise above-mentioned Fischer-Tropsch synthetic water is carried out to pre-warmed step, preferably above-mentioned Fischer-Tropsch synthetic water is preheated to 70～90 DEG C.By Fischer-Tropsch synthetic water being heated in advance or being approached the required temperature of dealcoholation treatment, shorten the dealcoholation treatment time, and then shorten the Fischer-Tropsch synthetic water treatment process cycle, improve the processing efficiency for the treatment of unit.
In above-mentioned dealcoholation treatment of the present invention, those skilled in the art can select suitable method to remove processing according to actual production conditions, in a kind of preferred embodiment of the present invention, adopt the mode of distillation to carry out dealcoholation treatment, the method of distillation is simple and convenient, and can effectively separate with heavy alcohol light alcohols.More preferably the temperature of above-mentioned distillation is 100～150 DEG C, and pressure is 0.1～0.3MPa, further preferred 0.2MPa.The temperature and pressure of distillation is controlled in above-mentioned scope, make light alcohols in Fischer-Tropsch synthetic water and separating of heavy alcohol more abundant, in remaining dealcoholysis water, the content of alcohol is relatively still less.
Above-mentioned treatment process of the present invention can make light alcohols, heavy alcohol separate from Fischer-Tropsch synthetic water, obtains relatively pure dealcoholysis water, follow-up to organic acid extraction treatment to facilitate.In order further to improve the purity of the heavy alcohol of separating, in another preferred embodiment of the present invention, above-mentioned treatment process also comprises washes to above-mentioned heavy alcohol isolate the process that obtains heavy alcohol.Make carried secretly a small amount of light alcohols water-soluble by washing, thereby realize and the separating of heavy alcohol.
In the another kind of preferred embodiment of the present invention, the process of above-mentioned washing comprises: above-mentioned heavy alcohol isolate is cooled to 35～45 DEG C; Above-mentioned heavy alcohol isolate after cooling is washed, obtained heavy alcohol and water wash water; Above-mentioned washing water is returned to above-mentioned steps S1.This water-washing method is washed after first heavy alcohol isolate being lowered the temperature again, is conducive to reduce the consumption of water.More preferably, above-mentioned heavy alcohol isolate is cooled to 40 DEG C and washes, be more conducive to reduce the consumption of water.Light alcohols soluble in water can reclaim a small amount of light alcohols wherein containing again by dealcoholation treatment step again, has improved the rate of recovery of light alcohols in Fischer-Tropsch synthetic water.
Further illustrate below in conjunction with specific embodiments beneficial effect of the present invention.
It should be noted that, the Fischer-Tropsch synthetic water shown in the equal his-and-hers watches 1 of the following example 1～4 is processed, and its character is in table 1.
The composition of table 1. Fischer-Tropsch synthetic water
| Composition | Massfraction/% | Composition | Massfraction/% |
| Acetaldehyde | 0.2709 | Amylalcohol | 0.7286 |
| Acetone | 0.0710 | Hexanol | 0.0879 |
| Butanone | 0.1070 | Acetic acid | 1.6293 |
| Methyl alcohol | 1.4076 | Propionic acid | 0.3747 |
| Ethanol | 2.8083 | Butyric acid | 0.2088 |
| Propyl alcohol | 1.4015 | Valeric acid | 0.0796 |
| Butanols | 0.7415 | Water | 90.0833 |
Embodiment 1
Taking the Fischer-Tropsch synthetic water shown in table 1 as raw material, press the device shown in Fig. 1, Fischer-Tropsch synthetic water is first heated to 83 DEG C through tube still heater, then entering distillation tower distills, controlling tower top temperature is 110 DEG C, pressure is 0.2MPa, and column bottom temperature is controlled at 124 DEG C, and lateral line withdrawal function is controlled at 115 DEG C.Tower top is isolated light alcohols, and its composition is in table 2.
Lateral line withdrawal function heavy alcohol isolate, enters water wash column 8 after being cooled to 40 DEG C, through washing, isolates heavy alcohol from tower top, and its component is in table 3; A small amount of light alcohols that heavy alcohol isolate is carried secretly is soluble in water after washing, reenters tube still heater heat with washing water, then through distillation again, light alcohols wherein can be separated.
Distillation tower tower bottom flow goes out dealcoholysis water, and its composition is in table 4.Dealcoholysis water enters organic acid extraction tower 3 along dealcoholysis water pipeline, as extraction agent, the organic acid in dealcoholysis water is extracted with trioctylamine, and the temperature of extraction is 35 DEG C; Pressure is 0.5MPa.Organic acid extraction tower 3 tower tops are isolated acid-bearing extractant, separate organic acid (being mainly acetic acid, propionic acid, butyric acid and valeric acid) and extraction agent through extraction agent recovery system, extraction agent can be recycled, and organic acid is sold or entered hydrotreater and produces liquefied gas and petroleum naphtha and fuel gas.At the bottom of organic acid extraction tower 3 towers, separate depickling waste water, chief component is in table 5.
In order further to reclaim a small amount of extraction agent containing in depickling water, depickling water is introduced in slurry tank, fully after sedimentation, isolate containing extraction waste water at slurry tank top, enter organic acid extraction tower 3 containing extraction waste water along containing the circulation of extraction waste line, the organic acid that may contain in extraction agent is re-started to extraction, improve organic acid percentage extraction.Isolate without extraction waste water slurry tank bottom, and because not containing other impurity, a part is as the wash water of water wash column 8, most of for the water distribution of gasification coal water slurry.
Embodiment 2
Taking the Fischer-Tropsch synthetic water shown in table 1 as raw material, by the device shown in Fig. 1, Fischer-Tropsch synthetic water is first heated to 70 DEG C through tube still heater, enter tower and distill, controlling tower top temperature is 115 DEG C, and pressure is 0.1MPa, column bottom temperature is controlled at 130 DEG C, and lateral line withdrawal function is controlled at 120 DEG C.Tower top is isolated light alcohols, and its composition is in table 2.
Lateral line withdrawal function heavy alcohol isolate, enters water wash column 8 after being cooled to 35 DEG C, through washing, isolates heavy alcohol from tower top, and its component is in table 3; A small amount of light alcohols that heavy alcohol isolate is carried secretly is soluble in water after washing, reenters tube still heater heat with washing water, then through again arranging, light alcohols wherein can be separated.
Distillation tower tower bottom flow goes out dealcoholysis water, and its composition is in table 4.Dealcoholysis water enters organic acid extraction tower 3 along dealcoholysis water pipeline, as extraction agent, the organic acid in dealcoholysis water is extracted with tributyl phosphate, and the temperature of extraction is 30 DEG C; Pressure is 0.3MPa.Organic acid extraction tower 3 tower tops are isolated acid-bearing extractant, separate organic acid (being mainly acetic acid, propionic acid, butyric acid and valeric acid) and extraction agent through extraction agent recovery system, extraction agent can be recycled, and organic acid is sold or entered hydrotreater and produces liquefied gas and petroleum naphtha and fuel gas.At the bottom of organic acid extraction tower 3 towers, separate depickling waste water, chief component is in table 5.
For the progressive a small amount of extraction agent containing in depickling water that reclaims, depickling water is introduced in slurry tank, fully after sedimentation, isolate containing extraction waste water at slurry tank top, enter organic acid extraction tower 3 containing extraction waste water along containing the circulation of extraction waste line, the organic acid that may contain in extraction agent is re-started to extraction, improve organic acid percentage extraction.Isolate without extraction waste water slurry tank bottom, and because not containing other impurity, a part is as the wash water of water wash column 8, most of for the water distribution of gasification coal water slurry.
Embodiment 3
Taking the Fischer-Tropsch synthetic water shown in table 1 as raw material, by the device shown in Fig. 1, Fischer-Tropsch synthetic water is first heated to 95 DEG C through tube still heater, enter distillation tower and distill, controlling tower top temperature is 120 DEG C, and pressure is 0.35MPa, column bottom temperature is controlled at 150 DEG C, and order-checking is extracted out and is controlled at 125 DEG C.Tower top is isolated light alcohols, and its composition is in table 2.
Lateral line withdrawal function heavy alcohol isolate, enters water wash column 8 after being cooled to 45 DEG C, through washing, isolates heavy alcohol from tower top, and its component is in table 3; A small amount of light alcohols that heavy alcohol isolate is carried secretly is soluble in water after washing, reenters tube still heater heat with washing water, then through again arranging, light alcohols wherein can be separated.
Distillation tower tower bottom flow goes out dealcoholysis water, and its composition is in table 4.Dealcoholysis water enters organic acid extraction tower 3 along dealcoholysis water pipeline, as extraction agent, the organic acid in dealcoholysis water is extracted with trioctylamine, and the temperature of extraction is 40 DEG C; Pressure is 0.8MPa.Organic acid extraction tower 3 tower tops are isolated acid-bearing extractant, separate organic acid (being mainly acetic acid, propionic acid, butyric acid and valeric acid) and extraction agent through extraction agent recovery system, extraction agent can be recycled, and organic acid is sold or entered hydrotreater and produces liquefied gas and petroleum naphtha and fuel gas.At the bottom of organic acid extraction tower 3 towers, separate depickling waste water, chief component is in table 5.
For the progressive a small amount of extraction agent containing in depickling water that reclaims, depickling water is introduced in slurry tank, fully after sedimentation, isolate containing extraction waste water at slurry tank top, enter organic acid extraction tower 3 containing extraction waste water along containing the circulation of extraction waste line, the organic acid that may contain in extraction agent is re-started to extraction, improve organic acid percentage extraction.Isolate without extraction waste water slurry tank bottom, and because not containing other impurity, a part is as the wash water of water wash column 8, most of for the water distribution of gasification coal water slurry.
Embodiment 4
Taking the Fischer-Tropsch synthetic water shown in table 1 as raw material, press the device shown in Fig. 1, Fischer-Tropsch synthetic water is first heated to 50 DEG C through tube still heater, entering distillation tower distills, controlling tower top temperature is 120 DEG C, pressure is 0.05MPa, and column bottom temperature is controlled at 160 DEG C, and lateral line withdrawal function temperature is controlled at 125 DEG C.
Lateral line withdrawal function heavy alcohol isolate, its component is in table 3; After being cooled to 65 DEG C, enter water wash column 8, through washing, isolate heavy alcohol from tower top, its component is in table 3; A small amount of light alcohols that heavy alcohol isolate is carried secretly is soluble in water after washing, reenters tube still heater heat with washing water, then through distillation again, light alcohols wherein can be separated.
Distillation tower tower bottom flow goes out dealcoholysis water, and its composition is in table 4.Dealcoholysis water enters organic acid extraction tower 3 along dealcoholysis water pipeline, uses ethyl acetate. and as extraction agent, the organic acid in dealcoholysis water is extracted, the temperature of extraction is 60 DEG C; Pressure is 1.5MPa.Organic acid extraction tower 3 tower tops are isolated acid-bearing extractant, separate organic acid (being mainly acetic acid, propionic acid, butyric acid and valeric acid) and extraction agent through extraction agent recovery system, extraction agent can be recycled, and organic acid is sold or entered hydrotreater and produces liquefied gas, petroleum naphtha and fuel gas.At the bottom of organic acid extraction tower tower, separate depickling waste water, chief component is in table 5.
For the progressive a small amount of extraction agent containing in depickling water that reclaims, depickling water is introduced in slurry tank, fully after sedimentation, isolate containing extraction waste water at slurry tank top, enter organic acid extraction tower 3 containing extraction waste water along containing the circulation of extraction waste line, the organic acid that may contain in extraction agent is re-started to extraction, improve organic acid percentage extraction.Isolate without extraction waste water slurry tank bottom, and because not containing other impurity, a part is as the wash water of water wash column 8, most of for the water distribution of gasification coal water slurry.
Table 2. light alcohols composition (wt/%)
| Composition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Acetaldehyde | 3.005 | 1.5 | 1.7 | 0 |
| Acetone | 0.788 | 0.939 | 0.835 | 0.215 |
| Butanone | 1.185 | 1.413 | 1.255 | 0.325 |
| Methyl alcohol | 15.554 | 20.544 | 17.130 | 4.305 |
| Ethanol | 31.155 | 38.144 | 33.005 | 8.593 |
| Propyl alcohol | 15.548 | 18.537 | 17.124 | 4.286 |
| Butanols | 7.436 | 0.01 | 7.878 | 2.267 |
| Amylalcohol | 1.001 | 0.004 | 1.060 | 0.012 |
| Water | 24.313 | 18.909 | 20.013 | 79.99 |
Table 3. heavy alcohol composition (wt/%)
| Composition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 3 | Embodiment 4 |
| Butanone | 0.019 | 0.019 | 0.018 | 0.019 | 0.001 |
| Butanols | 7.869 | 7.869 | 45.47 | 6.911 | 0.004 |
| Amylalcohol | 70.454 | 70.454 | 42.48 | 71.339 | 78.126 |
| Hexanol | 9.569 | 9.569 | 4.27 | 9.689 | 9.074 |
| Propionic acid | 0.0013 | 0.0013 | 0.0010 | 0.0010 | 0.8 |
| Water | 12.087 | 12.087 | 16.319 | 12.041 | 11.995 |
Table 4. dealcoholysis water composition (wt/%)
| Composition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Methyl alcohol | 0.0045 | 0.0044 | 0.0043 | 0.0061 |
| Acetic acid | 1.324 | 1.325 | 1.325 | 1.893 |
| Propionic acid | 0.305 | 0.306 | 0.306 | 0.437 |
| Butyric acid | 0.170 | 0.168 | 0.171 | 0.244 |
| Valeric acid | 0.065 | 0.067 | 0.064 | 0.101 |
| Amylalcohol | —— | 0.028 | —— | —— |
| Hexanol | —— | 0.031 | —— | —— |
| Water | 98.133 | 98.071 | 98.135 | 97.319 |
Table 5. depickling waste water composition (wt/%)
| Composition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Extraction agent | 0.012 | 0.101 | 0.0122 | 0.203 |
| Organic acid | 0.03 | 0.035 | 0.031 | 0.053 |
| Water | 99.958 | 99.846 | 99.956 | 99.762 |
Can find out from the data of above-mentioned table 2～table 5, the above embodiment of the present invention compared with prior art, the invention has the advantages that organism is reclaimed thoroughly, make full use of the value of synthetic water, economic benefit is high, and waste water, not containing other impurity, is conducive to synthetic wastewater recycling; Heavy alcohol water wash column adopts synthetic wastewater after treatment to replace de-mineralized water as wash water, has reduced the consumption of de-mineralized water, is conducive to reduction operation cost, and the simple easy handling of technique.To middle-size and small-size Fischer-Tropsch synthesizer synthetic water, processing is a desirable operational path.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (20)
1. a treatment unit for Fischer-Tropsch synthetic water, is characterized in that, described treatment unit comprises:
Dealcoholysis system (1), in order to remove light alcohols and the heavy alcohol in described Fischer-Tropsch synthetic water;
Extracting system (2), is connected by dealcoholysis water pipeline with described dealcoholysis system (1), in order to extract from the organic acid in the dealcoholysis water of described dealcoholysis system (1).
2. treatment unit according to claim 1, it is characterized in that, described extracting system (2) comprises that organic acid extraction tower (3), in order to extract the organic acid in described dealcoholysis water, is connected by dealcoholysis water pipeline with described dealcoholysis system (1).
3. treatment unit according to claim 1, it is characterized in that, described extracting system (2) also comprises that extraction agent recovery unit (4) is to reclaim extraction agent, between described extraction agent recovery unit (4) and described organic acid extraction tower (3), be provided with extraction liquid pipeline, described extraction liquid pipeline is delivered to described extraction agent recovery unit (4) in order to will extract organic acid extraction liquid.
4. treatment unit according to claim 3, it is characterized in that, between described organic acid extraction tower (3) and described extraction agent recovery unit (4), be also provided with extraction agent pipeline, the extraction agent of recovery is transmitted back to described organic acid extraction tower (3) by described extraction agent pipeline.
5. treatment unit according to claim 1, it is characterized in that, described extracting system (2) also comprises extraction wastewater sedimentation unit (5), in order to the water in extraction wastewater is separated with extraction agent, described extraction wastewater sedimentation unit (5) is connected by extraction wastewater pipeline with described organic acid extraction tower (3).
6. treatment unit according to claim 5, it is characterized in that, between described extraction wastewater sedimentation unit (5) and described organic acid extraction tower (3), be provided with containing extraction waste line described extraction wastewater sedimentation unit (5) is obtained to be transmitted back to described organic acid extraction tower (3) containing extraction waste water.
7. according to the treatment unit described in any one in claim 1 to 6, it is characterized in that, described dealcoholysis system (1) comprises dealcoholysis unit (6), between described dealcoholysis unit (6) and described extracting system (2), is connected by described dealcoholysis water pipeline.
8. treatment unit according to claim 7, is characterized in that, described dealcoholysis unit (6) comprising:
Dealcoholize column (7), and between described extracting system (2), be provided with described dealcoholysis water pipeline;
Water wash column (8), in order to the heavy alcohol isolate from described dealcoholize column (7) is washed, and is provided with heavy alcohol pipeline between described dealcoholize column (7).
9. treatment unit according to claim 8, it is characterized in that, described dealcoholysis system (1) also comprises that heat exchange unit (9) is in order to described Fischer-Tropsch synthetic water is carried out to preheating, and is provided with synthetic water pipeline between described dealcoholize column (7).
10. treatment unit according to claim 9, it is characterized in that, between described dealcoholize column (7) and described heat exchange unit (9), be provided with the hot steam of hot steam pipeline in order to carry described dealcoholize column (7) to produce to described heat exchange unit (9).
11. treatment unit according to claim 9, it is characterized in that, between described water wash column (8) and described heat exchange unit (9), also arrange by washing water recovery line and be delivered to described heat exchange unit (9) in order to the washing water that described water wash column (8) is produced.
The treatment process of 12. 1 kinds of Fischer-Tropsch synthetic waters, is characterized in that, the treating method comprises:
Step S1, described Fischer-Tropsch synthetic water is carried out to dealcoholation treatment, obtain dealcoholysis water, light alcohols isolate and heavy alcohol isolate;
Step S2, described dealcoholysis water is extracted, obtain depickling water and organic acid isolate.
13. treatment processs according to claim 12, is characterized in that, in described step S2, the extraction agent that described extraction adopts is selected from one or more in the group of tributyl phosphate, ethyl acetate and trioctylamine composition.
14. treatment processs according to claim 12, is characterized in that, in described step S2, the temperature of described extraction is 30～40 DEG C; Pressure is 0.3～0.8MPa.
15. treatment processs according to claim 12, is characterized in that, after described step S2, described treatment process also comprises:
Described organic acid isolate is carried out to extraction agent recycling, obtain organic acid and extraction agent;
Described extraction agent is returned to described step S2.
16. treatment processs according to claim 12, is characterized in that, after described step S2, described treatment process also comprises:
Described depickling waste water is carried out to sedimentation processing, obtain containing extraction waste water with without extraction waste water;
Return to described step S2 by described containing extraction waste water.
17. treatment processs according to claim 12, is characterized in that, before described step S1, described treatment process also comprises carries out pre-warmed step to described Fischer-Tropsch synthetic water, preferably described Fischer-Tropsch synthetic water is preheated to 70～95 DEG C.
18. treatment processs according to claim 12, is characterized in that, the dealcoholation treatment in described step S1 adopts the mode of distillation to carry out, and the temperature of preferred described distillation is 110～150 DEG C, and pressure is 0.1～0.35MPa, preferably 0.2MPa.
19. treatment processs according to claim 12, is characterized in that, described treatment process also comprises washes to described heavy alcohol isolate the process that obtains heavy alcohol.
20. treatment processs according to claim 19, is characterized in that, the process of described washing comprises:
Described heavy alcohol isolate is cooled to 35～45 DEG C;
Described heavy alcohol isolate after cooling is washed, obtained heavy alcohol and water wash water;
Described washing water is returned to described step S1.
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