CN117923589A - Method for extracting aromatic hydrocarbon in sewage by using dual-purpose extractant - Google Patents
Method for extracting aromatic hydrocarbon in sewage by using dual-purpose extractant Download PDFInfo
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- 239000010865 sewage Substances 0.000 title claims abstract description 245
- 238000000034 method Methods 0.000 title claims abstract description 201
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 60
- 238000000605 extraction Methods 0.000 claims abstract description 369
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 281
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 45
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A method for extracting aromatic hydrocarbon in sewage by using a dual-purpose extractant, wherein the sewage F10 containing aromatic hydrocarbon and phenol is subjected to an extraction process E100 using the dual-purpose extractant JY to obtain primary purified water, a special extractant regeneration process is not needed, so that investment is saved, energy consumption is reduced, a narrow fraction, a low molecular weight product and/or a circulating hydrocarbon stream existing in a fractionating tower UT system in a fractionating process of the dual-purpose extractant JY for hydrogenation stabilization reaction of hydrogen solvent to generate oil, such as middle-section reflux oil of a fractionating tower with a conventional boiling point of 120-250 ℃, top reflux oil of the fractionating tower with a conventional boiling point of 30-140 ℃, and the dual-purpose extractant returns to the fractionating tower UT to complete regeneration and multi-product separation recovery of the extract, thereby forming a combined process of the extraction process and the fractionating process; the hydrocarbon oil in the primary purified water can be extracted by a small amount of supplemental extractant with high hydrogen saturation in the supplemental extraction process, and the supplemental extractant is rich and usually finally enters the hydrogenation reaction process to finish the purification.
Description
Technical Field
The invention relates to a method for extracting aromatic hydrocarbon in sewage by using a dual-purpose extractant, which is particularly suitable for the primary extraction process of sewage containing aromatic hydrocarbon, phenol and other organic impurities generated in the direct liquefaction process of coal hydrogenation.
Background
Herein, wt% means weight%.
The invention relates to a coal hydrogenation direct liquefaction reaction process R10, which is a hydrogenation direct liquefaction reaction process taking coal oil slurry as a raw material and comprises a coal oil co-refining process of the coal oil slurry prepared by heavy oil (such as residual oil) and coal dust.
The hydrogen supply solvent hydrogenation stabilization reaction process R20 refers to a hydrogenation process of converting hydrocarbon oil separated from the generated oil in the hydrogen supply solvent hydrogenation stabilization reaction process R20 of hydrocarbon material flow generated by the hydrogenation direct liquefaction reaction process R10 into hydrogen supply solvent oil for preparing raw oil coal slurry in the coal supply hydrogenation direct liquefaction reaction process R10.
The hydro-upgrading reaction process R30 refers to a process for producing hydrocarbon oil with high hydrogen saturation by deep hydrogenation based on oil generated in a hydrogenation direct liquefaction reaction process R10 and/or oil generated in a hydrogenation stabilization reaction process R20 of a hydrogen-supplying solvent, wherein all impurity components (organic oxygen, organic sulfur, organic nitrogen, chlorine and fluorine) in reaction raw materials are almost removed, the aromatic hydrocarbon is saturated by large-scale hydrogenation, the hydrogen content of a hydro-upgrading naphtha product is usually 13.5-14.7 wt%, and the hydrogen content of a hydro-upgrading diesel product is usually 13.5-14.2 wt%. Regarding the hydrogen content of the high hydrogen saturation product of the hydro-upgrading reaction process R30 and the hydrocarbon component, one document describing such data is found in document a01: ① Publication name: direct coal liquefaction process and engineering, pages 415 to 430; ② The searching book codes: ISBN coding: 9-78703-04308-23; ③, incorporated: wu Xiuzhang, shu Geping, li Kejian, xie Shunmin; ④ Press: scientific press.
The extractant of the present invention is also referred to as extract oil; the term extractant is used in the invention, so that the concept distinction between the extractant and the oil dissolved in the sewage is facilitated.
The invention uses the concept of extraction to describe the process of reducing organic matters in wastewater by using the process that the extractant is hydrocarbon oil with higher hydrogen saturation, smaller molecular weight, lower density and lower organic oxygen content relative to the extraction target component, and the process of reducing organic matters in wastewater by using the process that the extractant is hydrocarbon oil with higher molecular weight, lower density and lower organic oxygen content is based on the fact that the attraction between molecules of the extraction target component (aromatic hydrocarbon and heteroatom-containing hydrocarbon have higher power supply) and water molecules has higher attraction between saturated hydrocarbon molecules with equal carbon number and water molecules, and compared with the set stripping rate of saturated hydrocarbon with equal concentration, the process that the set stripping rate of equal carbon aromatic hydrocarbon with equal concentration and wastewater with heteroatom-containing hydrocarbon with equal value is realized, and more extractant is needed.
The dual-purpose extractant of the invention is usually a process hydrocarbon stream with lower phenol concentration, lower boiling range and lower aromatic hydrocarbon content, and can be a narrow fraction, a low molecular weight and large flow rate recycle hydrocarbon stream such as a crude naphtha product at the top of a fractionating tower UT or a cold reflux of a reflux tank in a conventional fractionating tower with the boiling point of 30-140 ℃ and a cold recycle oil at the top of the fractionating tower with the boiling point of 120-200 ℃ and a cold reflux oil at the middle part of the fractionating tower, which are present in a fractionating process for generating oil by hydrogenation direct liquefaction of coal, a low molecular weight and large flow rate hydrocarbon stream such as a crude naphtha product at the top of the primary fractionating tower with the boiling point of 30-140 ℃ or a cold reflux oil at the reflux tank in a conventional fractionating tower with the boiling point of 120-200 ℃, and a cold recycle oil at the top of the primary fractionating tower with the boiling point of 120-200 ℃.
The invention mainly aims to provide a low-cost method suitable for a primary extraction process E100 of sewage containing aromatic hydrocarbon, phenol and other organic impurities generated in a coal hydrogenation direct liquefaction process, and the method can also be used as a primary purification method of other high-concentration sewage containing aromatic hydrocarbon and phenol, and of course, the method can also be used for treating other sewage with similar compositions, wherein the sewage can be cold high-molecular acidic water, cold low-molecular acidic water, normal pressure fractionating tower top water, vacuum fractionating tower evacuation system condensed water and tower top water generated in the coal hydrogenation direct liquefaction process, and the sewage can also be cold high-molecular acidic water and cold low-molecular acidic water of a solvent oil hydrogenation stabilizing device matched with a coal hydrogenation direct liquefaction device, and the sewage can also be tower top sewage of a coal tar fractionating tower or sewage generated in a coal gasification process.
The extractant of the sewage is an oil product or a solvent which takes the oil product as a main body and is blended with other components with stronger phenol dissolving capacity.
The hydrocarbon oil with lower phenol content, lower carbon number and higher hydrogen content is used as an extracting agent, so that part of hydrocarbon oil with higher carbon number and lower hydrogen content in the sewage can be transferred to the rich extracting agent, and the aim of partial deoiling of the sewage is fulfilled.
Meanwhile, the extractant of the common sewage also has a certain function of removing phenol, and one document for recording such data is shown in document A02: ① Publication name: modern handbook of coal chemical industry, pages 841 to 848; ② The searching book codes: ISBN coding: 978-7-122-09636-4; ③ master code: he Yongde; ④ Press: chemical industry publishers; page 841 of document a02 specifies that there are various conventional extractants for extracting dephenolization from sewage, one being heavy benzene (rich in monocyclic aromatic hydrocarbons with conventional boiling point of 100-130 ℃) and one being a mixed solvent (N503 (5-12 wt%) + kerosene), the purpose of this information being to demonstrate that the dual purpose extractant of the present invention also has a certain dephenolization effect.
For the detailed properties of cold high-purity oil in a state of phase equilibrium with sewage (cold high-purity water) containing organic impurities such as aromatic hydrocarbons and phenols in a coal hydrogenation direct liquefaction process, one document describing such data is found in document a01: ① Publication name: direct coal liquefaction process and engineering, pages 280 to 287; ② The searching book codes: ISBN coding: 9-78703-04308-23; ③, incorporated: wu Xiuzhang, shu Geping, li Kejian, xie Shunmin; ④ Press: scientific press.
Table 1A is the coal liquefaction crude oil (hydro-stabilized feedstock) properties of the Shenhua group coal direct liquefaction test and commercial unit.
Table 1B shows the ratios of the fractions of the coal-liquefied oil obtained in the coal liquefaction test of Shenhua group BSU.
Table 1C shows the properties of the fraction of coal liquefaction oil < 145 ℃ obtained by the coal liquefaction test of Shenhua group BSU.
Table 1D shows the properties of coal-liquefied kerosene and diesel oil fractions obtained in the coal liquefaction test of Shenhua group BSU.
Table 1E shows the hydrocarbon compositions of the coal-liquefied kerosene and diesel oil fractions obtained in the coal liquefaction test of Shenhua group BSU.
Table 1F shows the properties of fractions at 350-400℃and > 400℃of coal liquefaction oil obtained by the coal liquefaction test of Shenhua group BSU.
Table 1G shows the compositions of hydrocarbon fractions at 350-450 ℃ and > 400 ℃ in coal liquefaction oil obtained by coal liquefaction test of Shenhua group BSU.
Table 1H is a summary of hydrocarbon class compositions for different coal liquefaction oil fractions obtained from the Shenhua group BSU coal liquefaction test.
As can be seen from Table 1H, different coal liquefied oil fractions obtained from the coal liquefaction test of Shenhua group BSU have organic oxygen content more than 1.0wt% as the fractions become heavier, wherein the organic oxygen content of the fraction at 145-220 ℃ is up to 3.75wt%, so that cold high-water must contain phenols in a wide fraction range, and contain a large amount of phenols with boiling ranges of 145-220 ℃, and the coexistence of phenol oil can cause the solution to be emulsified.
As can be seen from Table 1H, the fraction at 220-350℃has a density of 0.9566g/cm 3 at 20℃and the fraction at 350-400℃has a density of 1.0192g/cm 3 at 20℃and the difference between the density value of water at 20℃and the density value of water at 0.9982g/cm 3 is only-0.0416 g/cm 3、0.021g/cm3, respectively, and the effect of separating oil from water by sedimentation separation is extremely poor for these components in addition to the emulsifying action of the oil, phenol and water solutions.
As can be seen from Table 1H, as the fraction becomes heavier, the saturated hydrocarbon ratio rapidly decreases and the total aromatics, polycyclic aromatics and gum content rapidly increases, and since the cold high-fraction oil contains a fraction of hydrocarbons of 350 to 400 ℃, the cold high-fraction water must contain bicyclic aromatics and tricyclic aromatics, and is highly likely to contain a small amount of tricyclic aromatics and a small amount of gum, and the separation effect by centrifugal separation is also not ideal for these components.
Table 1A properties of coal liquefaction crude oil (hydro-stabilized feedstock) for direct liquefaction test and commercial setup of Shenhua group coal
TABLE 1B ratio of fractions of coal-liquefied oil obtained by coal liquefaction test of Shenhua group BSU
| Flow range/. Degree.C | ＜145 | 145～220 | 220～350 | 350～400 | ＞400 | Totals to |
| Yield/wt% | 5.05 | 10.75 | 54.95 | 16.05 | 13.20 | 100.00 |
TABLE 1C properties of fractions of coal liquefaction oil < 145 ℃ obtained by coal liquefaction test of Shenhua group BSU
Table 1D Properties of coal liquefied kerosene and Diesel oil fractions obtained by coal liquefaction test of Shenhua group BSU
Table 1E coal liquefied kerosene and diesel fraction hydrocarbon composition (unit: wt%) obtained in coal liquefaction test of Shenhua group BSU
TABLE 1 properties of fractions at 350-400℃and > 400℃of coal liquefaction oil obtained by coal liquefaction test of Shenhua group BSU
TABLE 1G coal liquefaction test of Shenhua group BSU coal liquefaction oil 350-450 ℃ and > 400 ℃ fraction hydrocarbon composition (unit: wt%)
TABLE 1H hydrocarbon class composition summary of different coal liquefaction oil fractions obtained by the Shenhua group BSU coal liquefaction test
| Sequence number | Distillate distillation range, DEG C | ＜145 | 145～220 | 220～350 | 350～400 | ＞400 |
| 1 | Classification component | |||||
| 1.1 | Paraffin, wt% | 28.92 | 10.6 | 11.8 | 15.3 | 2.2 |
| 1.2 | Naphthene, wt% | 47.84 | 57.9 | 18.0 | 2.8 | 2.1 |
| 1.3 | Olefins, wt% | 12.90 | ||||
| 1.4 | Monocyclic aromatic hydrocarbon, wt% | 8.35 | 23.3 | 31.3 | 10.7 | 5.9 |
| 1.5 | Bicyclic aromatic hydrocarbons, wt% | 2.1 | 27.9 | 16.7 | 8.4 | |
| 1.6 | Tricyclic aromatic hydrocarbons, wt% | 3.0 | 17.1 | 11.7 | ||
| 1.7 | Tetracyclic aromatic hydrocarbons, wt% | 15.6 | 19.5 | |||
| 1.8 | Pentacyclic arene, wt% | 0.1 | 4.7 | |||
| 1.9 | Thiophene, wt% | 4.4 | 5.4 | |||
| 1.10 | Unidentified aromatic hydrocarbon, wt% | 1.4 | 8.3 | |||
| 1.11 | Colloid, wt% | 6.1 | 8.0 | 12.9 | 31.8 | |
| 2 | Classification statistics | |||||
| 2.1 | Saturated hydrocarbon, wt% | 76.76 | 68.5 | 29.8 | 18.1 | 4.3 |
| 2.2 | Olefins, wt% | 12.90 | ||||
| 2.3 | Aromatic hydrocarbon, wt% | 8.35 | 25.4 | 62.2 | 66.0 | 69.3 |
| 2.4 | Colloid, wt% | 6.1 | 8.0 | 12.9 | 31.8 | |
| 3 | Density at 20 ℃, g/cm 3 | 0.7548 | 0.8933 | 0.9566 | 1.0192 | 1.1102 |
| 4 | Organic oxygen, wt% | 1.51 | 3.75 | 1.09 | 1.28 | 1.82 |
| 5 | Organic S, μg/g | 286 | 212 | 114 | 2100 | 3300 |
| 6 | Organic N, μg/g | 1329 | 2228 | 2026 | 4500 | 10000 |
| 7 | Carbon residue, wt% | ＜0.02 | 4.23 | |||
| 8 | N-heptane insolubles, wt% | 2.20 | 19.60 | |||
| 9 | Hydrogen content, wt% | 11.10 | 10.54 | 9.08 | 7.63 |
Regarding the nature and quantity of wastewater containing aromatic hydrocarbons, phenols and other organic impurities produced in the coal hydrogenation direct liquefaction process, one document describing such data is found in document a01: ① Publication name: direct coal liquefaction process and engineering, pages 767 to 768; ② The searching book codes: ISBN coding: 9-78703-04308-23; ③, incorporated: wu Xiuzhang, shu Geping, li Kejian, xie Shunmin; ④ Press: scientific press. Table 2A is a statistical table of sour water sources, amounts and contaminants of direct coal liquefaction plants for coal hydrogenation in Shenhua Erdos coal oil company.
Table 2A table of statistics of acid water source, amount and contaminants of direct coal hydrogenation liquefaction device for oil-producing company of Shenyan Erdos coal
Taking the acid water of the direct coal hydrogenation liquefaction device of Shenhua Erdos coal oil company as listed in Table 2A as an example, wherein the oil content is 1900.3kg/h and the volatile phenol is 446.5kg/h, the sewage has the following characteristics:
① The acidic water of the direct coal hydrogenation liquefaction device is from a cold high-pressure separator and a cold low-pressure separator, and the balanced oil phase is cold high-fraction oil and cold low-fraction oil, wherein the cold high-fraction oil and the cold low-fraction oil contain dissolved gas, liquefied gas, naphtha components containing monocyclic aromatic hydrocarbon, diesel components containing dicyclic aromatic hydrocarbon, heavy diesel components containing tricyclic aromatic hydrocarbon, wax oil components containing tricyclic aromatic hydrocarbon and tetracyclic aromatic hydrocarbon, and contain a large amount of phenols; because the aromatic hydrocarbon, especially the dicyclic aromatic hydrocarbon, the tricyclic aromatic hydrocarbon and the tetracyclic aromatic hydrocarbon have great effect with water molecules, the solubility in water is high, and the deep separation is difficult to realize by adopting a standing method; the phenols have polarity, have high solubility in water and can form azeotropes with water, so that the phenomenon that the cold high-water-content and cold low-water-content of the direct coal hydrogenation liquefaction device contain high-concentration aromatic hydrocarbon and phenols is normal;
② The phenolic wastewater belongs to a foaming system, and the phenolic wastewater is easy to generate 'emulsion' when the phenolic wastewater contains a large amount of high aromatic hydrocarbon oil.
For the above reasons, it is generally difficult to efficiently remove oils and volatile phenols from the acidic water of a coal hydrogenation direct liquefaction plant at low cost, such as a stationary sedimentation separation method, and it is difficult to deeply separate an oil phase from an aqueous phase.
The extraction method is a traditional and effective sewage deoiling method, and partial phenols can be removed, however, the traditional extraction method using a special extractant has the following problems of complex flow and high cost when being applied to deoiling and devolatilizing the acidic water of a coal hydrogenation direct liquefaction device:
① Deep removal of oils of a wide range of molecular weight distribution requires 2 or more extraction steps in series using a relatively lighter hydrocarbon oil extractant
Because the cold high-fraction oil and the cold low-fraction oil contain dissolved gas, liquefied gas, naphtha component containing monocyclic aromatic hydrocarbon, diesel component containing dicyclic aromatic hydrocarbon, heavy diesel component containing tricyclic aromatic hydrocarbon, wax oil component containing tricyclic aromatic hydrocarbon and tetracyclic aromatic hydrocarbon, the acidic water A1 of the coal liquefaction device in the table 2A contains aromatic hydrocarbon and phenols with wide molecular weight distribution, and in order to deeply remove the aromatic hydrocarbon with wide molecular weight range and the phenols with wide molecular weight range in the acidic water A1 in the table 2A, the step-by-step gradual fractional extraction from large-molecular hydrocarbon to small-molecular-hydrocarbon (such as firstly removing aromatic hydrocarbon with the conventional boiling point of 250-420 ℃, secondly removing aromatic hydrocarbon with the conventional boiling point of 150-250 ℃ and finally removing aromatic hydrocarbon and naphthene with the conventional boiling point of 50-150 ℃) is needed, and accordingly, a step-by-step reduction of molecular weight fractional extractant is needed;
The analysis shows that the extraction process of deoiling and dephenolizing the acidic water of the coal hydrogenation direct liquefaction device is a multi-stage extraction process with complex flow;
in order to ensure the extraction effect, i.e. to limit the concentration of hydrocarbon oil in the purified water after extraction to be below a certain low level value, it is necessary to reduce the concentration of the extraction target component of the fresh extractant at the end extraction step of any extraction process, and to reduce the concentration of the extraction target component of the rich extract in the equilibrium state, i.e. to require a suitably large difference between the dry point of the distillation range of the fresh extractant and the boiling point of the extraction target component;
the above analysis shows that there should be a suitably large difference between the dry point of the distillation range of the fresh extractant and the boiling point of the extraction target component for each extraction process, i.e., the extractant should have a lower boiling point and a lower molecular weight than the extraction target component;
② Extractant requiring large flow rate ratios
The water/agent weight ratio K33 refers to the ratio of the weight flow rate of the sewage feed used in the extraction process to the weight flow rate of the fresh extractant; the larger the water/agent weight ratio K33 in the extraction process is, the more the number of extraction target components carried in the unit weight of the rich extractant is, the smaller the weight flow rate of the fresh extractant is, the smaller the scale of the rich extractant regeneration system is, the lower the energy consumption is, and the investment and the energy consumption are reduced; conversely, the smaller the water/agent weight ratio K333 in the extraction process, the smaller the amount of the extraction target component carried in the unit weight of the rich extractant, the more the fresh extractant weight flow rate, the larger the scale of the rich extractant regeneration system and the higher the energy consumption, and the investment and the energy consumption are necessarily increased under the same extraction task;
Based on the reason that the attraction between the molecules of the extraction target components (aromatic hydrocarbon and heteroatom-containing hydrocarbon have larger power supply property) and the water molecules is larger than the attraction between the molecules of the saturated hydrocarbon with equal carbon number and the water molecules, compared with the set stripping rate of the saturated hydrocarbon with equal concentration, the extraction process of realizing the set stripping rate of the equal value of the sewage with equal carbon aromatic hydrocarbon and heteroatom-containing hydrocarbon with equal concentration requires more extractant, namely the weight ratio K44 of the fresh extractant to take a proper larger value; in other words, a large agent/water weight ratio K44 extraction operation requiring multiple extractants is costly;
③ Regeneration system requiring multiple, large flow rates of rich extractant
Obviously, due to the large acid water flow rate of the coal hydrogenation direct liquefaction device, a high-agent/water ratio multistage extraction process formed by adopting a special extractant needs to be configured with a large-scale complex regeneration process of multiple rich extractants, and because the extractant components in the rich extractants are polluted by multiple extraction target components, the ideal extractant regeneration process necessarily requires multiple fractionating towers, thus a complex fractionating system is formed, and the investment is huge;
④ The energy consumption of the rich extractant regeneration system is high
It is obvious that, because the acidic water flow rate of the coal hydrogenation direct liquefaction device is very large, a multi-stage extraction process with high agent/water ratio formed by adopting a special extractant needs to be configured with a large-scale complex regeneration process of various rich extractants, and because extractant components in the rich extractants are polluted by various extraction target components, the ideal extractant regeneration process necessarily requires a plurality of fractionating towers, thus a complex large-scale fractionating system is formed, and the extractant must be subjected to a pervaporation process to realize separation from the extraction target components with higher boiling points, and the energy consumption of the fractionating system is necessarily huge;
⑤ How to maintain the stability of the components of the extractant contaminated by various aromatic hydrocarbons and various phenols
Because the extractant is polluted by the extraction target components in the same boiling range, the extractant and the extraction target components are extremely difficult to completely separate, and in order to separate a small amount of extraction target components with boiling points higher than the dry point of the extractant, the distillation separation method requires that all the extractant is subjected to an evaporation process, and the cost is too high to implement;
the above analysis shows that contamination of the extractant is a necessary consequence, requiring that the extractant must be replaced in large quantities in time (in the extreme, at any time) in order to maintain the composition of the extractant stable, i.e. that a large amount of fresh extractant is consumed;
⑥ Contaminated extractant-rich outlet
Consuming a large amount of fresh extractant, and consequently producing a large amount of contaminated rich extractant at the same time, this solution is not viable if the rich extractant is not used continuously in a reasonable large volume;
In summary, the conventional extraction method using the special extractant is not suitable for the extraction process E100 of the sewage D containing organic impurities such as aromatic hydrocarbon and phenol generated in the direct liquefaction process of coal hydrogenation.
If the effective preliminary deoiling treatment cannot be realized on the sewage containing aromatic hydrocarbon, phenol and other organic impurities generated in the coal hydrogenation direct liquefaction process, the treatment of the process U90 such as deamination, dehydrosulfuration, dephenolization and the like on the downstream of the sewage containing aromatic hydrocarbon, phenol and other organic impurities generated in the coal hydrogenation direct liquefaction process can be caused to have adverse effects, otherwise, if an effective preliminary deoiling method can be found, the operation of the process U90 can be greatly improved, the deoiling load of the process U90 can be reduced, the normal load rate and the continuous operation period of the device can be improved, and the quality of products (liquid ammonia, hydrogen sulfide and crude phenol) can be improved.
In theory, if an extraction agent of a suitable high flow rate can be found that does not require a dedicated regeneration process at the cost of being inexpensive, the "extraction system + extraction agent regeneration system" will evolve into a "separate extraction system", whereas the extraction system requires only an atmospheric vessel, mixer and/or extraction column, pump and a small amount of electricity consumption, which will be a reliable, low cost, economical method, with the problem that the "extraction agent that does not require a dedicated regeneration process" is present where the dual purpose extraction agent is.
The process of using the dual-purpose extractant at least meets the following requirements:
① As intermediate materials with proper distillation ranges, such as a fractionating tower system for generating oil in a hydrogenation stabilization reaction process R20 of a hydrogen solvent, a narrow fraction product needs to enter a hydro-upgrading reaction process R30 for deep hydro-processing, and a light narrow fraction product of the fractionating tower, a reflux liquid of a tower top reflux tank, a cold reflux circulating oil at the top of the tower and a cold reflux circulating oil at the middle section of the tower belong to intermediate materials with proper distillation ranges;
② The continuous and stable existence, such as a fractionating tower system for generating oil in the hydrogen solvent hydrogenation stabilization reaction process R20, wherein a narrow fraction product needs to enter the hydro-upgrading reaction process R30 for deep hydro-processing, and a return liquid reflux of a tower top reflux tank of the fractionating tower, a cold reflux circulating oil at the top part of the tower and a cold reflux circulating oil at the middle section of the tower belong to continuously and stably existing materials;
③ A large flow rate, such as a fractionating tower system for generating oil in a hydrogen solvent hydrogenation stabilization reaction process R20, wherein a small part of narrow fraction products need to enter a hydro-upgrading reaction process R30 for deep hydro-processing, and most other narrow fraction products are used as slurry oil slurry solvent oil in a coal hydrogenation direct liquefaction reaction process R10, and fractions with proper boiling points in the materials, such as fractions with conventional boiling points lower than 250 ℃, are suitable for serving as a dual-purpose extractant under a proper temperature state; on the other hand, the narrow fraction and low molecular weight recycle hydrocarbon streams existing in the fractionating tower UT system in the fractionating process of the hydrogen solvent hydrogenation stabilization reaction generated oil, such as fractionating tower middle section reflux oil JY1 with the conventional boiling point between 120 and 250 ℃ and fractionating tower top reflux oil JY2 with the conventional boiling point between 30 and 140 ℃, have large flow rate, and the streams comprise the reflux of the reflux liquid of the tower top reflux tank of the fractionating tower, the cold reflux recycle oil of the tower top and the cold reflux recycle oil of the tower middle section, and belong to large flow rate materials.
Document a01: ① Publication name: direct coal liquefaction process and engineering, pages 362 to 363; ② The searching book codes: ISBN coding: 9-78703-04308-23; ③, incorporated: wu Xiuzhang, shu Geping, li Kejian, xie Shunmin; ④ Press: scientific press. The design operation parameters of a fractionating tower of a hydrogenation stabilizing device matched with a Shenhua group 108 ten thousand tons/year coal hydrogenation direct liquefaction project are recorded.
Table 3A is a summary of the main operating parameters of the solvent oil hydrostabilizer fractionation column for the Shenhua group, wherein:
first, the cold reflux flow rate of the reflux drum returned to the tower is 67486kg/h;
Second, the reflux flow rate of the middle section of light distillate with the conventional boiling range of 145-220 ℃ is 63972kg/h, and the temperature conditions are as follows: the extraction temperature is 178.9 ℃, the reflux tower temperature is 54 ℃, the circulating cooling temperature difference is 124.9 ℃, if the reflux circulating cooling temperature difference of the middle section of the light distillate oil is reduced to 30 ℃, the reflux flow rate of the middle section of the light distillate oil is about 4.16 times of 63972kg/h, namely 266337kg/h, if the reflux circulating cooling temperature difference of the middle section of the light distillate oil is reduced to 15 ℃, the reflux flow rate of the middle section of the light distillate oil is about 8.32 times of 63972kg/h, namely 532674kg/h, and only the reflux oil of the middle section of the light distillate oil is formed, so that the oil/water weight ratio of 0.740, 3.08 and 6.15 is formed for the acid water source, the quantity and the sewage quantity 86.492kg/h listed in the pollutant statistics table of the direct hydrogenation liquefaction device for oil-making company of Shenhuados coal in Table 2A'; the middle reflux of the light distillate with the conventional boiling range of 145-220 ℃ can be split into 2 distillates with different boiling ranges, such as middle reflux with the conventional boiling range of 145-195 ℃ and the conventional boiling range of 170-220 ℃ according to the requirement;
④ The generated oil in the hydrogenation stabilization reaction process continuously enters a fractionating tower of a hydrogenation stabilization device to produce a new dual-purpose extractant,
Replacing the polluted dual-purpose extractant, and keeping the composition of the dual-purpose extractant stable;
⑤ The regeneration of the dual-purpose extractant and the processing of the extract are completed by virtue of other fractionating systems, and the rich dual-purpose extractant can continuously enter the original downstream position (the hydro-upgrading reaction process and the fractionating tower of the hydro-stabilizing device) to complete the regeneration of the dual-purpose extractant and/or the processing of the dual-purpose extractant.
TABLE 3A main operating parameter summary table for solvent oil hydrostabilization device fractionation columns for Shenhua group
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The following is combined with the requirements of the extraction process of cold high-molecular acid water generated in the coal hydrogenation direct liquefaction process on the composition of an extractant, the composition and properties of reaction generated oil of a hydrogen-supplying solvent hydrogenation stabilizing device matched with the coal hydrogenation direct liquefaction device and a narrow fraction circulating stream existing in the fractionation process are analyzed in detail, and one document recording the data is disclosed in document A01: ① Publication name: direct coal liquefaction process and engineering, pages 287 to 292; ② The searching book codes: ISBN coding: 9-78703-04308-23; ③, incorporated: wu Xiuzhang, shu Geping, li Kejian, xie Shunmin; ④ Press: scientific press.
Table 4A is a comparison table of properties of the directly liquefied oil a, a Shenhua group coal, a hydro-stabilized feedstock and a hydro-stabilized product, and it can be seen that the following significant changes occur after the hydro-stabilized feedstock is subjected to the hydro-stabilization treatment:
① The density at 20 ℃ is reduced from 0.9156g/cm 3 to 0.8784g/cm 3, and 0.0372g/cm 3 is reduced;
② The organic sulfur content is reduced from 630 mug/g to 18 mug/g, which is reduced by 97.1%;
③ The organic nitrogen content is reduced from 2246 mug/g to 648 mug/g, which is reduced by 71.1%;
④ The organic oxygen content is reduced from 1.81wt% to 0.50wt%, and is reduced by 72.4%;
⑤ The hydrogen content is increased from 10.55wt% to 11.55wt%, and is increased by 1.00wt%;
⑥ The boiling point of each distillation point is reduced by 20-35 ℃.
Obviously, compared with the Shenhua group coal direct liquefied oil A, the hydrogenation stable product of the Shenhua group coal direct liquefied oil A: the content of organic oxygen is reduced by 72.4 percent, so that the content of phenol is greatly reduced; the hydrogen content is increased by 1.00 weight percent, so that the saturation is increased, the aromaticity is reduced, the organic sulfur content is reduced by 97.1 percent, the organic nitrogen content is reduced by 71.1 percent, the organic oxygen content is reduced by 72.4 percent, the content of polar components is reduced, and the solubility of the oil product in water can be greatly reduced; the density is reduced by 0.0372g/cm 3 at 20 ℃, which is beneficial to oil-water separation; the change of the indexes shows that the hydrogenation stable product of the Shenhua group coal direct liquefaction oil A or the low boiling point distillate oil thereof is suitable for being used as an extractant of cold high-molecular acid water (acid water in balance with the Shenhua group coal direct liquefaction oil A) generated in the coal hydrogenation direct liquefaction process, can reduce the aromatic hydrocarbon content in the cold high-molecular acid water, and is also beneficial to reducing the phenol content in the cold high-molecular acid water.
Table 4B is a comparison table of properties of the hydrotropic feed and hydrotropic product of direct liquefaction oil B of Shenhua group coal, and it can be seen that the following significant changes occur in the coal liquefaction oil after the hydrotropic treatment:
① The density at 20 ℃ is reduced from 0.9962g/cm 3 to 0.9712g/cm 3, and the density is reduced by 0.025g/cm 3;
② The organic sulfur content is reduced from 184 mug/g to 0 mug/g, which is reduced by 100%;
③ The organic nitrogen content is reduced from 0.29wt% to 0.17wt%, which is reduced by 41.4%;
④ The organic oxygen content is reduced from 1.29wt% to 0.38wt%, by 70.5%;
⑤ The hydrogen content is increased from 9.40wt% to 10.15wt%, and the hydrogen content is increased by 0.75wt%;
⑥ The boiling point of each distillation point is reduced by 20-35 ℃.
Obviously, compared with the Shenhua group coal direct liquefied oil B, the hydrogenation stable product of the Shenhua group coal direct liquefied oil B: the content of organic oxygen is reduced by 70.5%, so that the content of phenol is greatly reduced; the hydrogen content is increased by 0.75 weight percent, so that the saturation is increased, the aromaticity is reduced, the organic sulfur content is reduced by 100 percent, the organic nitrogen content is reduced by 41.4 percent, the organic oxygen content is reduced by 70.5 percent, the content of polar components is reduced, and the solubility of the oil product in water can be greatly reduced; the density is reduced by 0.025g/cm 3 at 20 ℃, which is beneficial to oil-water separation; the change of the indexes shows that the hydrogenation stable product of the Shenhua group coal direct liquefaction oil B or the low boiling point distillate oil thereof is suitable for being used as an extractant of cold high-molecular acid water (acid water in balance with the Shenhua group coal direct liquefaction oil B) generated in the coal hydrogenation direct liquefaction process, can reduce the aromatic hydrocarbon content in the cold high-molecular acid water, and is also beneficial to reducing the phenol content in the cold high-molecular acid water.
Table 4C is the properties of the naphtha fraction of the solvent oil hydro-stabilization unit product of the group of shenhua, 6, 2012.
Table 4D is the properties of the light diesel fraction of the solvent oil hydro-stabilization device product of the shenhua group, 6, 2012.
Table 4E shows the product fraction properties of the direct liquefaction of oil A by Shenhua group coal.
Table 4F shows the fraction properties of the hydrogenated stabilized product < 220℃in the direct coal liquefaction pilot (BSU) coal liquefaction test of Shenhua group Shenhua.
Table 4G is the properties of the medium temperature solvents in the solvent oil hydro-stabilization device products of the shenhua group at 6 months 2012.
Table 4H shows the 220-350 ℃ distillate properties of the hydrogenated and stabilized product of the coal liquefaction test of Shenhua group BSU.
Table 4I is a summary of BSU coal liquefaction test for hydrocarbon class composition of the hydro-stabilized products of different fractions obtained from the Shenhua group BSU coal liquefaction test and commercial units.
Table 4A comparison table of properties of the hydrogenated stable feedstock and hydrogenated stable product of direct liquefaction of oil a from Shenhua group coal
Table 4B comparison of properties of the hydrogenated stable feedstock and hydrogenated stable product of direct liquefaction of oil B from Shenhua group coal
Table 4c properties of naphtha fraction from solvent oil hydro-stabilization unit for group of Shenhua in 2012
Table 4d properties of light diesel fraction of solvent oil hydro-stabilization device product of the group of Shenhua, 6 nd 2012
TABLE 4E product fraction Properties of direct liquefaction of oil A by Shenhua group coal hydrogenation stability test
TABLE 4F Shenhua group Shenhua coal direct liquefaction pilot (BSU) coal liquefaction test hydrogenation stabilization product < 220 ℃ distillate Properties
Table 4 properties of warm solvents in the product of the solvent oil hydro-stabilization device for the group of Shenhua, 6 th 2012
TABLE 4 properties of 220-350 ℃ distillate of hydrogenated and stabilized product of coal liquefaction test of Shenhua group BSU
TABLE 4I general table for BSU coal liquefaction test of Shenhua group of hydrocarbon class composition of the hydro-stabilized products of different fractions obtained from commercial units
| Sequence number | Distillate distillation range, DEG C | ＜145 | 145～220 | 220～350 |
| A first part | Hydrogenation stability- -BSU test data | |||
| 1 | Distillation Range ASTM D-86, DEG C | 78～170 | 121～233 | 218～347 |
| 2 | Density at 20 ℃, g/cm 3 | 0.7571 | 0.8434 | 0.9504 |
| 3 | Organic oxygen, wt% | 0.42 | 0.54 | |
| 4 | Organic S, μg/g | 4 | 67 | 263 |
| 5 | Organic N, μg/g | 81 | 142 | 1016 |
| 6 | Hydrogen content, wt% | 12.16 | 10.42 | |
| Two (II) | Hydro stabilization-commercial plant data | Naphtha fraction | Light diesel fraction | Medium temperature solvent |
| 1 | Distillation Range ASTM D-86, DEG C | 45～175 | 115～285 | 213～328 |
| 2 | Density at 20 ℃, g/cm 3 | 0.7473 | 0.8774 | 0.9256 |
| 3 | Organic oxygen, wt% | |||
| 4 | Organic S, μg/g | 31 | 24 | 50 |
| 5 | Organic N, μg/g | 230 | 410 | 470 |
| 6 | Hydrogen content, wt% | |||
| Three kinds of | Table 1H comparative examples of coal liquefaction oil quality | |||
| 1 | Distillation Range ASTM D-86, DEG C | 78～157 | 152～228 | 213～348 |
| 2 | Density at 20 ℃, g/cm 3 | 0.7548 | 0.8933 | 0.9566 |
| 3 | Organic oxygen, wt% | 1.51 | 3.75 | 1.09 |
| 4 | Organic S, μg/g | 286 | 212 | 114 |
| 5 | Organic N, μg/g | 1329 | 2228 | 2026 |
| 6 | Hydrogen content, wt% | 11.10 | 10.54 |
The analysis shows that the hydrogenation of the Shenhua group coal direct liquefaction oil is stable to generate light narrow fraction of the oil, and the light narrow fraction is a suitable extractant for cold high water distribution of a Shenhua group coal hydrogenation direct liquefaction device.
To this end, the basic idea of the invention has been proposed: a method for extracting aromatic hydrocarbon in sewage by using a dual-purpose extractant, wherein the sewage F10 containing aromatic hydrocarbon and phenol is subjected to an extraction process E100 using the dual-purpose extractant JY to obtain primary purified water, a special extractant regeneration process is not needed, so that investment is saved, energy consumption is reduced, a narrow fraction, a low molecular weight product and/or a circulating hydrocarbon stream existing in a fractionating tower UT system in a fractionating process of the dual-purpose extractant JY for hydrogenation stabilization reaction of hydrogen solvent to generate oil, such as middle-section reflux oil of a fractionating tower with a conventional boiling point of 120-250 ℃, top reflux oil of the fractionating tower with a conventional boiling point of 30-140 ℃, and the dual-purpose extractant returns to the fractionating tower UT to complete regeneration and multi-product separation recovery of the extract, thereby forming a combined process of the extraction process and the fractionating process; the hydrocarbon oil in the primary purified water can be extracted by a small amount of supplemental extractant with high hydrogen saturation in the supplemental extraction process, and the supplemental extractant is rich and usually finally enters the hydrogenation reaction process to finish the purification.
The method can be used for jointly processing various sewage with different compositions, the sewage can be mixed and then enters an extraction process, and the sewage can also be mixed and treated together with intermediate treatment water with the composition close to that of the intermediate extraction process of the sewage which is most difficult to extract according to the flow positions of different intermediate extraction steps of the extraction process of the sewage which is most difficult to extract respectively according to the specific concentration of the pollution components.
In the method, in the extraction process, double-purpose extractants with different compositions can be used jointly, for example, overhead reflux oil of an atmospheric fractionating tower for directly liquefying coal to generate oil (overhead reflux oil of the fractionating tower with conventional boiling point mainly consisting of hydrocarbon components at 30-140 ℃) can be used.
In the extraction process, the method of the invention has the following operating temperature range: typically 10-80 c, typically 20-60 c, preferably 30-50 c, and too low a temperature results in a high viscosity of the oil product, which is difficult to separate, and too high a temperature results in an excessively high partial pressure of water vapor, which results in the emission of waste gases.
In the process of the invention, the residence time required for any one particular extraction step in the extraction process is determined according to the actual operating requirements, for example by extraction experiments, and the residence time of the oil-water layer after extraction generally meets the layering requirement, usually 3 to 60 minutes, generally 5 to 40 minutes, preferably 5 to 10 ℃.
In the method, the density of the dual-purpose extractant is required to be lower than that of sewage in the extraction process, and the greater the difference ED10 between the density of the dual-purpose extractant and that of the sewage, the better, ED10 is usually more than 0.08, generally more than 0.12 and preferably more than 0.20, thereby being beneficial to accelerating the delamination of oil and water and facilitating the separation of pollutants from the water phase into the extractant.
In the method, the aromatic hydrocarbon concentration of the dual-purpose extractant is required to be proper in the extraction process, so that the similar compatibility is conveniently realized, the dissolution and transfer efficiency of the extractant to 'extracting target aromatic hydrocarbon and phenols' in sewage is improved, in the multiple extraction processes using multiple extractants, the aromatic degree of the downstream extractant is lower than that of the upstream extractant along with the deepening of the extraction process, and the supplemental extraction process E200 is expected to be established after the dual-purpose extraction process, the hydrocarbon concentration (the quantity of aromatic hydrocarbon in the purified water is reduced to the limit) of the primary purified water including the dual-purpose extractant JY is reduced by using a small quantity of the supplemental extractant, and the supplemental extractant is enriched to finally enter the hydrogenation reaction process to finish the purification.
The method is suitable for new design or modification of the existing device.
Compared with the conventional extraction deoiling method which needs to be provided with a special regeneration system for the rich extractant, the method has the advantages that the quantity of the special extractant can be reduced by 50-70%, even the special extractant is completely eliminated, namely, the special extractant is not used, and the special regeneration system for the rich extractant is not needed.
The invention aims to provide a method for extracting aromatic hydrocarbon in sewage by using a dual-purpose extractant.
The method combines a fractionating tower UT system for the fractionation process of generating oil by hydrogenation stabilization reaction of hydrogen solvent and a regeneration, supplement and discharge system of the rich extractant in the sewage extraction process to form a combined process, forms a complete process of combined extraction and rich extractant treatment, greatly reduces the investment and energy consumption of the rich extractant treatment system, belongs to a supplement or improvement or optimization of the integral process of coal hydrogenation direct liquefaction, has the following mutual influence of the operation conditions and design principles, and has the following mutual relation:
① According to the extraction requirement, setting the composition, flow rate, operating temperature and operating pressure of circulating oil materials of the fractionating tower UT system under the condition of not changing the functions of the fractionating tower UT system;
that is, only the flow rate, temperature or cooling process temperature difference of the recycle stream is changed without changing the property (composition) requirements of the direct-separation oil product (the direct liquefaction process of the coal removal hydrogenation is used as solvent oil and flushing oil, and the hydro-upgrading process of the hydrogen removal solvent is used as raw material oil) of the fractionating tower UT of the fractionating process;
② Setting the composition, flow rate, operation temperature and operation pressure of circulating oil materials of the fractionating tower UT system under the condition of not changing the overall function of the fractionating tower UT system according to the extraction requirement, and then, according to the property requirement of the final product of the fractionating process (the coal-removal hydrogenation direct liquefaction process is used as solvent oil and flushing oil, the hydrogen-removal solvent hydro-upgrading process is used as raw oil), the narrow fraction hydrocarbon oil leaving the fractionating tower UT from the fractionating tower is split and/or mixed to be combined into hydrocarbon oil materials with expected composition and flow rate;
That is, in order to achieve the optimum operation of the extraction process, changing the properties (composition of components) and flow rate of the direct-separation oil product (the direct liquefaction process of the decoking hydrogenation as solvent oil, flushing oil, the hydro-upgrading process of the decoking solvent as raw material oil) of the fractionating tower UT of the fractionation process, and then calling out the properties and flow rate of the desired final product (the direct liquefaction process of the decoking hydrogenation as solvent oil, flushing oil, the hydro-upgrading process of the decoking solvent as raw material oil) through a heat exchanger, a pipeline or a tank area, requires changing the properties, flow rate, temperature or cooling process temperature difference of the recycle stream of the fractionating tower UT.
The analysis shows that the fractionating tower UT system for generating oil by hydrogenation stabilization of the Shenhua group coal direct liquefaction oil exists an extractant with proper large flow rate required by the process of extracting dearomatization by the cold Gao Fenshui of the Shenhua group coal hydrogenation direct liquefaction device.
In the process of the invention, a fresh extractant is used in each extraction stage.
In each extraction section, the countercurrent contact and separation process of the extractant and the sewage can be carried out for 1 time or 2 times or more, and the countercurrent contact and separation process is called a 1-stage or 2-stage or multi-stage extraction process.
In each extraction section, the method of the invention uses a specific composition of feed extractant JYX, and the contact separation mode of feed water phase DW-and feed extractant JY-X is not limited, and any suitable mode can be adopted, and one or more of the following modes can be selected:
① One extraction section comprises single contact and single separation, wherein the water phase EFW-X and the extractant EFY-X are mixed and contacted to form a mixed flow EMS-X, and the EMS-X is separated into an extractant-rich phase EPY-X and a deoiled water phase EPW-X;
the mixing contact mode of the aqueous phase EFW-X and the extractant EFY-X is not limited, and a mixer can be used for forced mixing;
The EMS-X separation mode is not limited, and sedimentation separation, centrifugal separation and centrifugal separation plus sedimentation separation are generally adopted;
② One extraction section comprises 2 times of contact and 2 times of separation, and raw material water phase EFW-X and raw material extractant EFY-X are in countercurrent mixing contact;
In the first contact separation step, the raw material water phase EFW-X is mixed and contacted with the first intermediate extractant-rich EPY-X1 discharged in the second contact separation step to form a mixed flow EMS-X1, and the EMS-X1 is separated into a second extractant-rich phase EPY-X2 and a first deoiling water phase EPW-X1;
In the second contact separation step, the first deoiled water phase EPW-X1 is mixed and contacted with the raw material extractant EFY-X to form a mixed flow EMS-X2, and the EMS-X2 is separated into a first extractant-rich phase EPY-X1 and a second deoiled water phase EPW-X2;
③ One extraction section comprises 3 times of contact and 3 times of separation, and raw material water phase EFW-X and raw material extractant EFY-X are in countercurrent mixing contact;
In the first contact separation step, the raw material water phase EFW-X is mixed and contacted with the second intermediate extractant-rich EPY-X2 discharged in the second contact separation step to form a mixed flow EMS-X1, and the EMS-X1 is separated into a third extractant-rich phase EPY-X3 and a first deoiling water phase EPW-X1;
In the second contact separation step, the first de-oiled water phase EPW-X1 is mixed and contacted with the first intermediate extractant-rich EPY-X1 discharged in the third contact separation step to form a mixed flow EMS-X2, and the EMS-X2 is separated into a second extractant-rich phase EPY-X2 and a second de-oiled water phase EPW-X2;
In the third contact separation step, the second deoiled water phase EPW-X2 is mixed and contacted with the raw material extractant EFY-X to form a mixed flow EMS-X3, and the EMS-X3 is separated into a first extractant-rich phase EPY-X1 and a third deoiled water phase EPW-X3;
④ One extraction section comprises more than 3 times of countercurrent contact of sewage and an extractant and more than 3 times of oil-water separation;
⑤ Static extraction tower
In the extraction process using a static extraction column, the wastewater is in countercurrent contact with the extractant; ideally, the volumetric flow rate of the extractant is larger than the volumetric flow rate of the sewage, the extractant is used as a continuous phase, the sewage is used as a dispersed phase after being highly dispersed, the particle number of sewage liquid drops is increased, the diameter of the sewage particles is reduced, the phase transfer diffusion distance from a water phase to an extractant oil phase of the extraction target component of the sewage particles is shortened, the mass transfer surface area of the sewage liquid drops is increased, and the extraction efficiency is improved;
The mass transfer elements of the static extraction column may use trays and/or packing, typically trays;
a static extraction column is generally provided with a plurality of trays, such as 3 to 100 trays, generally 40 to 60 trays;
the static extraction tower can also use fillers, the fillers need to be distributed in multiple layers, and redistributor internals are needed to be arranged among the fillers so as to redistribute a descending water phase and an ascending extractant oil phase;
⑥ Turntable tower
In extraction processes using dynamic extraction columns such as a rotating disk column, the rotating disk acts as an agitator, typically a flat disk rotating disk; ideally, the volumetric flow rate of the extractant is larger than the volumetric flow rate of the sewage, the extractant is used as a continuous phase, the sewage is used as a dispersed phase after being highly dispersed, the particle number of sewage liquid drops is increased, the diameter of the sewage particles is reduced, the phase transfer diffusion distance from a water phase to an extractant oil phase of the extraction target component of the sewage particles is shortened, the mass transfer surface area of the sewage liquid drops is increased, and the extraction efficiency is improved;
dynamic extraction columns such as rotary tray columns, may also use a combination of stationary trays and/or packing;
Dynamic extraction columns are typically provided with a plurality of trays, such as 3 to 100 trays, typically 40 to 60 trays;
the dynamic extraction tower can also use fillers, the fillers need to be distributed in multiple layers, and redistributor internals are needed to be arranged among the fillers so as to redistribute a descending water phase and an ascending extractant oil phase;
The rotating speed of the turntable tower is determined according to experiments, and is generally 10-60 revolutions per minute, and is generally 20-40 revolutions per minute;
a rotary turntable is arranged in the dynamic tower, so as to strengthen the mixing effect between the oil phase and the water phase;
In a liquid-liquid system, the density difference between two phases is small, the interfacial tension is not large, the flow velocity of the two-phase liquid is not large, from the view of the process fluid mechanics condition, the inertial force which can be used for strengthening the process is not large in the contact process of the liquid and the dispersed two-phase layering separation capability is not high; therefore, in order to improve the efficiency of the liquid-liquid mass transfer device, measures such as stirring, pulsation, vibration and the like are often required to be adopted to supplement energy; to separate the phases, a layering stage is required to ensure sufficient residence time for the dispersed phases to coalesce. The external energy is introduced in the liquid-liquid mass transfer separation process, so that the liquid dispersion can be promoted, the two-phase flow contact condition is improved, the mass transfer in the process is facilitated, the mass transfer efficiency is improved, and the height of extraction equipment is reduced; however, it is also noted that if the applied energy is too large, the axial back mixing of the two-phase liquid in the device is aggravated, so that the mass transfer driving force in the process is reduced, and the mass transfer efficiency is reduced; in addition, the liquid drops are excessively dispersed and undersized, the internal circulation of the liquid drops is disappeared, and the mass transfer efficiency is also affected; therefore, when determining the external energy, the factors of both aspects of interest and disadvantage should be fully considered, and for a specific extraction process, the proper input energy should be determined through experiments (or device trial production and debugging), namely, the rotation number of the turntable motor needs to be adjusted according to the processing amount in the operation; the size of the liquid drops not only relates to the phase mass transfer area, but also influences the mass transfer coefficient and the flux of the extraction tower; when dispersing a dispersed phase liquid into droplets, it is necessary to take these two factors into consideration sufficiently; therefore, when the fluctuation of the processing amount is not large in the actual operation, the adjustment of the revolution of the turntable is not recommended, and the well-confirmed revolution at the beginning of the starting operation is maintained;
Regarding the control of the phase separation interface of the rotary disk extraction tower, when the extraction tower is started, continuous phase liquid is filled in the tower, then a disperse phase valve is opened to enable two-phase liquid to contact mass transfer in the tower, and disperse phase liquid drops can be discharged from the tower after condensation; when the light phase is used as a disperse phase, the disperse phase is condensed in a layered section at the top of the tower, and after the interface of the two phases is maintained at a proper height, a disperse phase outlet valve is opened to discharge light phase liquid from the tower; simultaneously, the sewage phase is arranged at the bottom of the extraction tower, and the interface height is automatically adjusted by means of an II-shaped pipe of a heavy phase outlet;
⑦ Extraction column for any other suitable column mass transfer internals
Other extraction process operating conditions include: operating pressure, operating temperature, phase density difference, and phase separation settling time.
The present invention, the dual extractant extraction process E100, comprises at least 1 stage dual extractant extraction process E1001, and generally comprises 2 stages of serially operated dual extractant extraction processes E1001, E1002 using different compositions, and may comprise 3 stages of serially operated dual extractant extraction processes E1001, E1002, E1003 using different compositions, and even further comprises 4 stages of serially operated dual extractant extraction processes E1001, E1002, E1003, E1004 using different compositions.
In the extraction process E100 with a dual-purpose extractant, 2 to 4 extraction stages with dual-purpose extractants of different compositions are usually provided, with the purpose of:
① 2-4 circulating dual-purpose extractants with different compositions, extracting hydrocarbon oil with different carbon numbers, wherein generally, sewage is firstly contacted with the dual-purpose extractant with the largest average carbon number of molecules, the dual-purpose extractant with the highest boiling range carries heavy hydrocarbon oil with the high boiling range into a lower UTL1 of a fractionating tower UT, the dual-purpose extractant with the lower boiling range carries hydrocarbon oil with the lower boiling range into a UTL2 of the fractionating tower UT, a mass transfer element is arranged at a UTL tower section of the fractionating tower between the UTL1 and the UTL2, the dual-purpose extractant with the higher boiling range carries hydrocarbon oil with the high boiling range into a UTL1 of the fractionating tower UT, and the pollution ratio of materials in the UTL2 of the fractionating tower UT is greatly reduced;
In a word, the quality of the narrow fraction oil products of the fractionating tower UT is improved;
② In the multi-stage sewage extraction process, the sewage is finally contacted with a light dual-purpose extractant with the average molecular carbon number of the least, the boiling range of the least and the conventional boiling point of less than 150 ℃ in general, and the light dual-purpose extractant has the lowest density, the lowest organic oxygen content and the lowest saturated solubility of hydrocarbon molecules in water in all dual-purpose extractants, so that the circulating dual-purpose extractant working system of 2-4 extraction stages has the advantages of low carbon number of the extractives carried by the light dual-purpose extractants and the lowest pollution degree of heavy hydrocarbons in the initial sewage raw materials, thereby the heavy hydrocarbon pollution degree brought to the narrow fraction products at the upper part of the fractionating tower UT is the lowest.
In the invention, a supplementary extraction process E200 is generally arranged, a small amount of supplementary extractant with high hydrogen saturation is used for extracting and reducing the quantity of the dual-purpose extractant JY in E100 purified sewage, and the rich supplementary extractant finally enters a hydrogenation reaction process to finish purification.
The supplementary extraction process E200 may be any supplementary extraction agent BY with a proper composition, and is generally composed of naphtha with high hydrogen saturation, for example, the hydro-modified naphtha with a conventional boiling range of 80-120 ℃ separated from the generated oil in the hydro-modification reaction process for producing deep hydro-modified oil matched with the coal hydrogenation direct liquefaction process is selected, the initial boiling point of the supplementary extraction agent BY cannot be too low so as to reduce the content of easily-evaporated light hydrocarbon components, namely, the saturated vapor pressure and the evaporation loss, and meanwhile, the dry distillation point of the supplementary extraction agent BY cannot be too high so as to reduce the solubility of the supplementary extraction agent BY in water, reduce the oil content of aquatic products, facilitate evaporation removal, and meanwhile, the higher the hydrogen saturation of the supplementary extraction agent BY is better so as to facilitate the processes of sedimentation separation deoiling, oxidative decomposition deoiling, bacterial digestion deoiling and the like in the later sewage deep treatment process.
The contact and separation mode of the water phase and the extractant in the supplementary extraction process E200 is not limited, and the working mode, the operating pressure and the operating temperature are almost the same as those of the extraction process E100.
The additional extraction process E200 generally provides a greater density differential between the extractant and the wastewater and a shorter settling time for phase separation than extraction process E100.
After extracting hydrocarbon components and phenol components in sewage by using the extractant, separating the extract (hydrocarbon oil and phenol transferred in the extraction process) in a fractionating tower UT by using the circulating type extractant JY1, and separating the extract into 2 or more narrow fraction products in the fractionating tower, wherein the composition of the narrow fraction product of a hydrocarbon stream S10 is slightly changed, and dehydration, non-condensable gas removal and conventional gas hydrocarbon removal are finished, but the purpose or subsequent processing path of the narrow fraction of the fractionating tower UT are basically not changed; the hydrocarbon stream based on single pass dual purpose extractant JY2 is combined into a fractionation process UT55 for the hydrogenation reaction and/or simultaneous processing of other hydrocarbon streams S10.
Because the problems are commonly existed in the whole process of large-scale coal hydrogenation direct liquefaction and the sewage flow is large, the invention has great economic value and general practicability.
Disclosure of Invention
The invention discloses a method for extracting aromatic hydrocarbon in sewage by using a dual-purpose extractant, which is characterized by comprising the following steps:
sewage F10, which contains aromatic hydrocarbon and phenol or not;
the extractant JY is used as the extractant with different compositions of 1 path or 2 paths or multiple paths of hydrocarbon;
⑴ In the extraction process E100, sewage F10-X based on sewage F10 and a dual-purpose extractant JY-X based on the dual-purpose extractant JY are mixed and contacted for at least one time to form a mixture flow E100-XM, and the mixture flow E100-XM is separated into a dual-purpose rich extractant RJY-X and de-oiled water F10P-X; the deoiled water product discharged from the extraction process E100 is used as primary purified water; the extraction process E100 discharges a rich and dual-purpose extractant product;
In the extraction process E100, the operation density of the extractant JY-X is lower than that of the sewage F10-X;
The weight flow rate of the hydrocarbon in the rich dual-purpose extractant RJY-X is higher than the weight flow rate of the hydrocarbon in the dual-purpose extractant JY-X;
The weight concentration of the hydrocarbon oil of the deoiling water F10P-X is lower than that of the hydrocarbon oil of the sewage F10-X;
The extracted wastewater finally leaving the extraction process E100 is used as primary purified water;
⑵ Treatment of Fu-dual purpose extractant RJY-X
The treatment of the rich and dual-purpose extractant RJY-X selects 1 or more of the following operation modes:
① Based on hydrocarbon material flow rich in the dual-purpose extractant RJY-X, the hydrocarbon material flow enters a fractionating tower UT for simultaneously processing other hydrocarbon material flows S10 to separate out the dual-purpose extractant JY for recycling, and the dual-purpose extractant JY belongs to the recycling dual-purpose extractant JY1;
a fractionation column UT separating 2 and or more narrow-cut hydrocarbon oils;
② Based on the hydrocarbon stream rich in the dual-purpose extractant RJY-X, entering a hydrogenation reaction process and/or entering a fractionation process U55 for simultaneously processing other hydrocarbon streams S55, wherein the fractionation process U55 does not produce the dual-purpose extractant JY, and the dual-purpose extractant JY belongs to the single-way dual-purpose extractant JY2;
the fractionation column UT55 of the fractionation process U55 separates 2 and or more narrow-cut hydrocarbon oils.
In the present invention, the weight flow rate of phenol in the rich dual-purpose extractant RJY-X is generally higher than that in the dual-purpose extractant JY-X;
The weight concentration of phenol in the deoiling water F10P-X is lower than that in the sewage F10-X.
In the present invention, ⑵ generally employs a fractionation column UT system in a dual extractant regeneration process;
A hydrocarbon stream based on oil generated in the coal hydrogenation direct liquefaction reaction process R10 is converted into a reaction effluent R20P in the hydrogenation stabilization reaction process R20 for producing hydrogen-donating solvent, and the hydrogenation stabilization reaction generated oil R20PY is obtained based on the reaction effluent R20P;
At least a portion of the hydrocarbon stream based on the hydrostabilization reaction to form oil R20PY is fed to fractionation column UT for distillative separation and at least 2 different fractions of hydrocarbon oil are separated.
The sewage F10 can be selected from one or more of the following materials:
① Cold high-molecular acid water in the coal hydrogenation direct liquefaction process;
② Cold low-pressure acidic water in the coal hydrogenation direct liquefaction process;
③ The coal hydrogenation direct liquefaction process generates sewage of the fractionation process of oil;
④ Cold high-molecular acid water of solvent oil hydrogenation stabilizing device matched with coal hydrogenation direct liquefying device;
⑤ Cold low-fraction acidic water of a solvent oil hydrogenation stabilizing device matched with a coal hydrogenation direct liquefying device;
⑥ The tower top sewage of the coal tar fractionating tower;
⑦ Sewage generated in the coal gasification process;
⑧ Other aromatic hydrocarbon-containing and phenol-containing sewage.
The invention discloses a single-pass type single-purpose ⑵ source of extractant JY2
Single pass dual purpose extractant JY2 is a narrow fraction, low molecular weight hydrocarbon stream from the hydrocarbon fractionation column T60 system;
fractionation column T60 of the hydrocarbonaceous material is not fractionation column UT55 nor UT of fractionation process U55;
the single-pass dual-purpose extractant JY2 can be selected from one or more of the following streams:
① The product of the top reflux drum of the fractionating tower T60 is selected from any one or more of the following:
Firstly, condensing and cooling tower top gas of a fractionating tower T60, and then entering a tower top reflux tank to separate out tower top reflux tank hydrocarbon oil, wherein at least a part of the tower top reflux tank hydrocarbon oil is used as a single-pass dual-purpose extractant JY2;
Secondly, the tower top gas of the fractionating tower T60 is subjected to 2-stage or multi-stage condensation, cooling and separation processes to generate 2 or more tower top condensate, and any one or more tower top condensate is/are used as a single-pass dual-purpose extractant JY2;
Thirdly, condensing and cooling the tower top gas of the fractionating tower T60, and then entering a tower top reflux tank to separate out hydrocarbon oil in the tower top reflux tank; at least one part of the light hydrocarbon-removed liquid obtained by heating and/or depressurizing hydrocarbon oil in the tower top reflux tank and then separating and fractionating is used as a single-pass dual-purpose extractant JY2;
② The top side draw of the fractionation column T60;
③ The middle side line of the fractionating tower T60 is used for extracting oil;
④ Other hydrocarbon oil products of the fractionation column T60.
In the process of regenerating the double-purpose extractant, the circulating double-purpose extractant JY1 of the invention ⑵ can be selected from one or more of the following materials:
① The reflux liquid from the reflux drum at the top of the fractionating tower UT is selected from one or more of the following streams:
Firstly, condensing and cooling tower top gas of a fractionating tower UT, and then entering a tower top reflux tank to separate out tower top reflux tank hydrocarbon oil, wherein at least part of the tower top reflux tank hydrocarbon oil returns to the top of the fractionating tower UT to become tower top reflux liquid RFX1;
at least a part of the tower top reflux liquid RFX1 is used as a circulating type dual-purpose extractant JY1;
Secondly, the tower top gas of the fractionating tower UT generates 2 or more tower top condensate liquid through 2-stage or multi-stage condensation cooling separation process, and any one or more tower top condensate liquid returns to the top of the fractionating tower UT to become tower top reflux liquid RFX2;
At least a part of the tower top reflux liquid RFX2 is used as a circulating type dual-purpose extractant JY1;
Thirdly, condensing and cooling tower top gas of the fractionating tower UT, and then entering a tower top reflux tank to separate out hydrocarbon oil in the tower top reflux tank; the hydrocarbon oil in the tower top reflux tank is subjected to a heating and/or depressurization process, and then is subjected to a separation and fractionation process to obtain a tower top condensate for removing light hydrocarbons; at least a portion of the light hydrocarbon-stripped overhead condensate is used as overhead reflux RFX3 and/or at least a portion of the light hydrocarbon-stripped overhead condensate is used as an effluent product;
at least a part of the tower top reflux liquid RFX3 is used as a circulating type dual-purpose extractant JY1;
② Cold circulating reflux liquid at the top of the fractionating tower UT;
The tower top cold circulation reflux mode refers to collecting liquid UT-L888 from an oil collecting device in the upper section of the fractionating tower UT, then enabling the liquid UT-L888 to leave the fractionating tower UT through a liquid outlet UT-L888-N, cooling the liquid through a cooling process, and returning the liquid to a mass transfer cooling section UT-TNC-01 at the uppermost end of the fractionating tower UT so as to enable at least part of rising hydrocarbon steam to be condensed into liquid; in the fractionating tower UT, a mass transfer cooling section UT-TNC-01 is positioned above a liquid outlet UT-L888-N of liquid UT-L888;
③ Reflux oil from the middle section of the fractionating tower UT;
④ Other hydrocarbon oil products of the fractionation column UT.
In general, the density of ⑵ at 20 ℃ of any one of the double-purpose extractants JY belongs to one of the following values:
①0.95～0.90g/cm3;②0.90～0.85g/cm3;③0.85～0.80g/cm3;④0.80～0.75g/cm3;
⑤＜0.75g/cm3。
in general, the organic oxygen content of the extracting agent JY used for any path of ⑵ belongs to one of the following values:
①0.70～0.55wt％;②0.55～0.40wt％;③＜0.40wt％。
In the present invention, generally, ⑵ any path of the extractant JY is used as the distillation range of ASTM D-86, the temperature of the distillation point is 5wt% to 95wt%, and the temperature belongs to one of the following values:
①80～130℃;②80～150℃;③80～170℃;④120～180℃;⑤130～180℃；
⑥140～180℃;⑦180～230℃;⑧190～230℃;⑨200～230℃;⑩210～260℃；
220～260℃；/>230～260℃；/>150～260℃；/>160～250℃；/>170～230℃。
in the present invention, generally, ⑴ in the extraction process E100, the ratio of the operation volume flow rate of the extractant JY-X to the operation volume flow rate of the sewage F10-X is the agent/water volume ratio K100 in the extraction process, and the value of the agent/water volume ratio K100 is one of the following values:
①10.0～5.0;②5.0～2.0;③2.0～1.0;④1.0～0.50；
⑤0.50～0.10;⑥0.10～0.01。
In general, the operating temperature of ⑴ extraction process E100 of the present invention is selected from one of the following data:
①10～20℃;②20～30℃;③30～40℃;④40～50℃;⑤50～60℃;⑥60～80℃。
In general, the operating pressure of ⑴ extraction process E100 according to the present invention is selected from one of the following data:
①0.0～0.1MPaG;②0.1～0.2MPaG;③0.2～0.3MPaG;④0.3～1.0MPaG。
In general, the operating objective of ⑴ extraction process E100 according to the present invention is expressed as the ratio of the weight concentration of hydrocarbon oil of de-oiled water F10P-X to the weight concentration of hydrocarbon oil of sewage F10-X, selected from one of the following data:
① 0.90 to 0.80 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 10 to 20 weight percent;
② 0.80 to 0.70 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 20 to 30 weight percent;
③ 0.70 to 0.60 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 30 to 40 weight percent;
④ 0.60 to 0.50 percent, namely, the removal rate of hydrocarbon oil in the sewage F10-X is 40 to 50 weight percent;
⑤ 0.50 to 0.40 percent, namely, the removal rate of hydrocarbon oil in the sewage F10-X is 50 to 60 weight percent;
⑥ 0.40 to 0.30 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 60 to 70 percent by weight;
⑦ 0.30 to 0.20 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 70 to 80 weight percent;
⑧ The removal rate of hydrocarbon oil in the sewage F10-X is more than 80wt percent.
In general, the aim of the present invention, ⑴ extraction process E100, is to select from one of the following data the ratio of the weight concentration of hydrocarbon oils with a conventional boiling point higher than 150℃for de-oiled water F10P-X to the weight concentration of hydrocarbon oils with a conventional boiling point higher than 150℃for sewage F10-X:
① 0.90 to 0.80 percent, namely the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is 10 to 20 weight percent;
② 0.80 to 0.70 percent, namely the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is 20 to 30 weight percent;
③ 0.70 to 0.60, namely, the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is 30 to 40 weight percent;
④ 0.60 to 0.50 percent, namely, the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is 40 to 50 percent by weight;
⑤ 0.50 to 0.40 percent, namely, the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is 50 to 60 weight percent;
⑥ 0.40 to 0.30 percent, namely the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is 60 to 70 percent by weight;
⑦ 0.30 to 0.20, namely, the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is 70 to 80 weight percent;
⑧ The removal rate of hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is less than 0.20 and is more than 80 weight percent.
In general, the aim of the present invention, ⑴ extraction process E100, is to select the ratio of the weight concentration of phenol of the de-oiled water F10P-X to the weight concentration of phenol of the sewage F10-X, from one of the following data:
① 0.90 to 0.80 percent, namely the removal rate of phenol in the sewage F10-X is 10 to 20 weight percent;
② 0.80 to 0.70 percent, namely the removal rate of phenol in the sewage F10-X is 20 to 30 weight percent;
③ 0.70 to 0.60, namely, the removal rate of phenol in the sewage F10-X is 30 to 40 weight percent;
④ 0.60 to 0.50 percent, namely the removal rate of phenol in the sewage F10-X is 40 to 50 percent by weight;
⑤ 0.50 to 0.40 percent, namely 50 to 60 percent of phenol in the sewage F10-X;
⑥ The removal rate of phenol in sewage F10-X is more than 60wt percent.
In the present invention, generally, ⑶ in the supplemental extraction process E200, the hydrocarbon oil containing the dual-purpose extractant JY in the primary purified water is extracted with the supplemental extractant 2PY with high hydrogen saturation;
in the supplementary extraction process E200, the sewage F20-X based on primary purified water and the extractant based on the supplementary extractant 2PY are mixed and contacted at least once to become a mixed stream E200-XM, and the mixed stream E200-XM is separated into the supplementary extractant 2PYP-X and the deoiled water F20P-X;
the operation density of the supplementary extractant 2PY is lower than that of the sewage F20-X;
the weight flow rate of hydrocarbons in the rich supplemental extractant 2PYP-X is higher than the weight flow rate of hydrocarbons in the supplemental extractant 2 PY;
the weight concentration of hydrocarbon oil in the deoiling water F20P-X is lower than that in the primary purified water sewage F20-X.
In general, the present invention, ⑷, is rich in the supplemental extractant 2PYP-X, in one or more of the following ways:
① Entering a coal hydrogenation direct liquefaction reaction process R10;
② The separation and fractionation process of the generated oil in the coal hydrogenation direct liquefaction reaction process R10 are carried out;
③ Entering a hydrogen-supplying solvent hydrogenation stabilization reaction process R20 for processing a hydrocarbon stream which is based on the oil generated by the coal hydrogenation direct liquefaction reaction process R10;
④ The separation and fractionation process of the generated oil of the hydrogen-supplying solvent hydrogenation stabilization reaction process R20 for processing the hydrocarbon stream based on the oil generated in the coal hydrogenation direct liquefaction reaction process R10;
⑤ Entering into fractionating tower UT;
⑥ Entering a hydro-upgrading reaction process R30 for processing a hydrocarbon stream which is based on the oil generated by the coal hydrogenation direct liquefaction reaction process R10;
⑦ A hydro-upgrading reaction process R30 for processing the hydrocarbon stream of the generated oil of the hydrogen-supplying solvent hydro-stabilization reaction process R20 based on the hydrocarbon stream of the generated oil of the coal hydrogenation direct liquefaction reaction process R10;
⑧ As absorption oil, the oil enters an absorption process of the rich gas to remove the liquefied gas component;
⑨ The absorption oil which is taken as absorption oil enters the absorption process of the rich gas and liquefied gas removal component is converted into rich absorption oil, and the rich absorption oil enters the hydrogenation reaction process.
In the present invention, ⑶ is a separation and fractionation process of the produced oil from the hydro-upgrading reaction process R30 in the supplemental extraction process E200 using the supplemental extractant 2 PY;
Hydrocarbon stream based on oil generated in the coal hydrogenation direct liquefaction reaction process R10 enters the hydro-upgrading reaction process R30, or
The hydrocarbon stream of the generated oil of the hydrogen supply solvent hydrogenation stabilization reaction process R20 based on the hydrocarbon stream of the generated oil of the coal hydrogenation direct liquefaction reaction process R10 enters the hydro-upgrading reaction process R30.
In the invention, ⑶ is generally used in the supplementary extraction process E200, and the density of the supplementary extracting agent 2PY at 20 ℃ is less than 0.80g/cm 3;
The dry point of the ASTM D-86 distillation range of the supplemental extractant 2PY is less than 180 ℃;
the organic oxygen content of the supplemental extractant 2PY is less than 0.05wt%;
the ratio of the operating volume flow rate of the supplemental extractant 2PY to the operating volume flow rate of the primary purified water is the agent/water volume ratio K200 of the supplemental extraction process, K200 being one of the following values:
①0.30～0.20;②0.20～0.10;③0.10～0.01；
The operation temperature of the supplementary extraction process E200 is 20-60 ℃;
the operating pressure of the supplementary extraction process E200 is 0.0 to 0.3MPaG.
In general, the aim of the operations of the ⑶ -up extraction process E200 according to the present invention is that the ratio of the weight concentration of hydrocarbon oil in the de-oiled water P20-X to the weight concentration of hydrocarbon oil in the primary purified water is selected from one of the following data:
① 0.90 to 0.80 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 10 to 20 weight percent;
② 0.80 to 0.70 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 20 to 30 weight percent;
③ 0.70 to 0.60 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 30 to 40 weight percent;
④ 0.60 to 0.50 percent, namely, the removal rate of hydrocarbon oil in the sewage F10-X is 40 to 50 weight percent;
⑤ 0.50 to 0.40 percent, namely, the removal rate of hydrocarbon oil in the sewage F10-X is 50 to 60 weight percent;
⑥ The removal rate of hydrocarbon oil in sewage F10-X is less than 0.40 and is more than 60 weight percent.
In general, the aim of the operation of the ⑶ -up extraction process E200 according to the present invention is that the ratio of the weight concentration of hydrocarbon oils with a conventional boiling point of the de-oiled water P20-X higher than 150℃to the weight concentration of hydrocarbon oils with a conventional boiling point of the primary purified water higher than 150℃is selected from one of the following data:
① Is 0.90 to 0.80, namely the removal rate of hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the primary purified water is 10 to 20 weight percent;
② Is 0.80 to 0.70, namely the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the primary purified water is 20 to 30 weight percent;
③ 0.70 to 0.60, namely, the removal rate of hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the primary purified water is 30 to 40 weight percent;
④ The removal rate of the hydrocarbon oil in the primary purified water is 0.60 to 0.50 percent, namely, the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the primary purified water is 40 to 50 percent by weight;
⑤ The removal rate of hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the primary purified water is more than 50wt percent, which is less than 0.50-0.40.
In the present invention, in general, a demulsifier mainly composed of carbon and hydrogen that can be converted by hydrogenation reaction is used in the extraction process E100 or the supplementary extraction process E200;
The demulsifier is used for breaking emulsified oil-water mixed liquid drops, so that at least partial separation of oil and water phases in the emulsified oil-water mixed liquid drops occurs, the demulsified and separated oil phase enters a main oil phase product of the extraction process E100 or the supplementary extraction process E200, and the demulsified and separated water phases enter a main water phase product of the extraction process E100 or the supplementary extraction process E200.
In the present invention, in general, in the extraction process E100 or the supplementary extraction process E200, there are at least 2 extraction stages using different extraction agents operated in series, and the main flow of the sewage is taken as the advancing direction, and the properties of the extraction agent used in the downstream extraction stage are 1 or several of the following characteristics compared with those of the extraction agent used in the upstream extraction stage;
① The density of the extractant used in the downstream extraction stage is lower than that of the extractant used in the upstream extraction stage;
② The dry point of the ASTM D-86 distillation range of the extractant used in the downstream extraction stage is lower than the dry point of the ASTM D-86 distillation range of the extractant used in the upstream extraction stage;
③ The organic oxygen content of the extractant used in the downstream extraction stage is lower than that of the extractant used in the upstream extraction stage;
④ The aromatic hydrocarbon content of the extractant used in the downstream extraction section is lower than that of the extractant used in the upstream extraction section;
⑤ The downstream extraction stage uses an extractant having a higher hydrogen content than the upstream extraction stage.
In general, according to the invention, at least one extraction stage is present in the extraction process E100 or in the supplemental extraction process E200;
the operation mode of the extraction section is selected from one or more of the following operation modes:
① One extraction section comprises single contact and single separation, raw material water EFW-X and raw material extractant EFY-X are mixed and contacted to form a mixed flow EMS-X, and the mixed flow EMS-X is separated into extractant-rich EPY-X and de-oiled water EPW-X;
the mixing and contacting process of the dehydrated water EPW-X and the raw material extractant EFY-X uses a mixer to forcedly mix;
the EMS-X separation mode of the mixture flow is selected from one or more of sedimentation separation and centrifugal separation;
② One extraction section comprises 2 countercurrent contacts and 2 separations, and raw water EFW-X and raw extractant EFY-X are in countercurrent mixed contact for 2 times;
In the first contact separation step, raw water EFW-X is mixed and contacted with a first intermediate extraction-rich agent EPY-X1 discharged in the second contact separation step to form a mixed flow EMS-X1, and the mixed flow EMS-X1 is separated into a second extraction-rich agent EPY-X2 and a first deoiling water EPW-X1;
In the second contact separation step, the first dehydrated water EPW-X1 is mixed and contacted with the raw material extractant EFY-X to form a mixed stream EMS-X2, and the mixed stream EMS-X2 is separated into a first extractant-rich EPY-X1 and a second dehydrated water EPW-X2;
③ One extraction section comprises 3 countercurrent contacts and 3 separations, and raw water EFW-X and raw extractant EFY-X are in countercurrent mixed contact for 3 times;
In the first contact separation step, raw water EFW-X and a second intermediate extraction-rich agent EPY-X2 discharged in the second contact separation step are mixed and contacted to form a mixed flow EMS-X1, and the mixed flow EMS-X1 is separated into a third extraction-rich agent EPY-X3 and a first deoiling water EPW-X1;
In the second contact separation step, the first oil removal water EPW-X1 is mixed and contacted with the first intermediate extraction agent EPY-X1 discharged in the third contact separation step to form a mixed flow EMS-X2, and the mixed flow EMS-X2 is separated into a second extraction agent EPY-X2 and a second oil removal water EPW-X2;
In the third contact separation step, the second dehydrated water EPW-X2 is mixed and contacted with the raw material extractant EFY-X to form a mixed stream EMS-X3, and the mixed stream EMS-X3 is separated into a first extractant-rich EPY-X1 and a third dehydrated water EPW-X3;
④ One extraction section comprises more than 3 times of countercurrent contact of sewage and an extractant and more than 3 times of oil-water separation;
⑤ Static internal extraction tower
The extraction process uses an extraction tower of a static tower internal part, and sewage and an extractant are subjected to countercurrent contact separation for a plurality of times;
When the volume flow rate of the extractant is larger than the volume flow rate of the sewage, the extractant is used as a continuous phase, the sewage is dispersed by the distributor and then used as a dispersed phase, and the sewage is dispersed by the distributor to increase the particle number of sewage liquid drops and reduce the diameter of sewage particles;
mass transfer elements of static extraction columns using trays and/or packing;
Static extraction towers, the number of trays is usually 3-100, and typically 40-60;
when the static extraction tower uses the filler, the filler is distributed in multiple layers, and redistributor internals are arranged between the filler layers to redistribute the descending water phase and the ascending extractant oil phase;
⑥ Dynamic internal extraction tower
The extraction process uses an extraction tower of dynamic tower internals, and the extraction tower of the dynamic tower internals uses a turntable or other dynamic tower internals;
when the inner rotary table is used in the dynamic column inner extraction column, the rotary table serves as a stirrer, and is a flat-disc rotary table or other rotary tables;
When the volume flow rate of the extractant is larger than the volume flow rate of the sewage, the extractant is used as a continuous phase, the sewage is dispersed by the distributor and then used as a dispersed phase, and the sewage is dispersed by the distributor to increase the particle number of sewage liquid drops and reduce the diameter of sewage particles;
extraction columns for dynamic column internals, with or without stationary trays and/or packing layers;
when the inner tower rotating disc is used in the extraction tower of the dynamic tower internals, the number of the inner tower rotating disc is usually 3-100, and is usually 40-60;
When the packing is used in the extraction tower of the dynamic tower internals, the packing is distributed in a plurality of layers, and redistributing internals are arranged among the packing layers to redistribute the descending water phase and the ascending extractant oil phase;
the rotation speed of the turntable is usually 10 to 60 rpm, and is usually 20 to 40 rpm.
In the present invention, at least one extraction mass transfer section using an extraction column, which is a rotating disc type extraction column, is generally present in the extraction process E100 or the supplementary extraction process E200, and the number of rotatable trays of the mass transfer section of the rotating disc type extraction column is 20 to 100.
Detailed Description
The invention discloses a method for extracting aromatic hydrocarbon in sewage by using a dual-purpose extractant, which is characterized by comprising the following steps of:
the invention discloses a method for extracting aromatic hydrocarbon in sewage by using a dual-purpose extractant, which is characterized by comprising the following steps:
sewage F10, which contains aromatic hydrocarbon and phenol or not;
the extractant JY is used as the extractant with different compositions of 1 path or 2 paths or multiple paths of hydrocarbon;
⑴ In the extraction process E100, sewage F10-X based on sewage F10 and a dual-purpose extractant JY-X based on the dual-purpose extractant JY are mixed and contacted for at least one time to form a mixture flow E100-XM, and the mixture flow E100-XM is separated into a dual-purpose rich extractant RJY-X and de-oiled water F10P-X; the deoiled water product discharged from the extraction process E100 is used as primary purified water; the extraction process E100 discharges a rich and dual-purpose extractant product;
In the extraction process E100, the operation density of the extractant JY-X is lower than that of the sewage F10-X;
The weight flow rate of the hydrocarbon in the rich dual-purpose extractant RJY-X is higher than the weight flow rate of the hydrocarbon in the dual-purpose extractant JY-X;
The weight concentration of the hydrocarbon oil of the deoiling water F10P-X is lower than that of the hydrocarbon oil of the sewage F10-X;
The extracted wastewater finally leaving the extraction process E100 is used as primary purified water;
⑵ Treatment of Fu-dual purpose extractant RJY-X
The treatment of the rich and dual-purpose extractant RJY-X selects 1 or more of the following operation modes:
① Based on hydrocarbon material flow rich in the dual-purpose extractant RJY-X, the hydrocarbon material flow enters a fractionating tower UT for simultaneously processing other hydrocarbon material flows S10 to separate out the dual-purpose extractant JY for recycling, and the dual-purpose extractant JY belongs to the recycling dual-purpose extractant JY1;
a fractionation column UT separating 2 and or more narrow-cut hydrocarbon oils;
② Based on the hydrocarbon stream rich in the dual-purpose extractant RJY-X, entering a hydrogenation reaction process and/or entering a fractionation process U55 for simultaneously processing other hydrocarbon streams S55, wherein the fractionation process U55 does not produce the dual-purpose extractant JY, and the dual-purpose extractant JY belongs to the single-way dual-purpose extractant JY2;
the fractionation column UT55 of the fractionation process U55 separates 2 and or more narrow-cut hydrocarbon oils.
In the present invention, the weight flow rate of phenol in the rich dual-purpose extractant RJY-X is generally higher than that in the dual-purpose extractant JY-X;
The weight concentration of phenol in the deoiling water F10P-X is lower than that in the sewage F10-X.
In the present invention, ⑵ generally employs a fractionation column UT system in a dual extractant regeneration process;
A hydrocarbon stream based on oil generated in the coal hydrogenation direct liquefaction reaction process R10 is converted into a reaction effluent R20P in the hydrogenation stabilization reaction process R20 for producing hydrogen-donating solvent, and the hydrogenation stabilization reaction generated oil R20PY is obtained based on the reaction effluent R20P;
At least a portion of the hydrocarbon stream based on the hydrostabilization reaction to form oil R20PY is fed to fractionation column UT for distillative separation and at least 2 different fractions of hydrocarbon oil are separated.
The sewage F10 can be selected from one or more of the following materials:
① Cold high-molecular acid water in the coal hydrogenation direct liquefaction process;
② Cold low-pressure acidic water in the coal hydrogenation direct liquefaction process;
③ The coal hydrogenation direct liquefaction process generates sewage of the fractionation process of oil;
④ Cold high-molecular acid water of solvent oil hydrogenation stabilizing device matched with coal hydrogenation direct liquefying device;
⑤ Cold low-fraction acidic water of a solvent oil hydrogenation stabilizing device matched with a coal hydrogenation direct liquefying device;
⑥ The tower top sewage of the coal tar fractionating tower;
⑦ Sewage generated in the coal gasification process;
⑧ Other aromatic hydrocarbon-containing and phenol-containing sewage.
The invention discloses a single-pass type single-purpose ⑵ source of extractant JY2
Single pass dual purpose extractant JY2 is a narrow fraction, low molecular weight hydrocarbon stream from the hydrocarbon fractionation column T60 system;
fractionation column T60 of the hydrocarbonaceous material is not fractionation column UT55 nor UT of fractionation process U55;
the single-pass dual-purpose extractant JY2 can be selected from one or more of the following streams:
① The product of the top reflux drum of the fractionating tower T60 is selected from any one or more of the following:
Firstly, condensing and cooling tower top gas of a fractionating tower T60, and then entering a tower top reflux tank to separate out tower top reflux tank hydrocarbon oil, wherein at least a part of the tower top reflux tank hydrocarbon oil is used as a single-pass dual-purpose extractant JY2;
Secondly, the tower top gas of the fractionating tower T60 is subjected to 2-stage or multi-stage condensation, cooling and separation processes to generate 2 or more tower top condensate, and any one or more tower top condensate is/are used as a single-pass dual-purpose extractant JY2;
Thirdly, condensing and cooling the tower top gas of the fractionating tower T60, and then entering a tower top reflux tank to separate out hydrocarbon oil in the tower top reflux tank; at least one part of the light hydrocarbon-removed liquid obtained by heating and/or depressurizing hydrocarbon oil in the tower top reflux tank and then separating and fractionating is used as a single-pass dual-purpose extractant JY2;
② The top side draw of the fractionation column T60;
③ The middle side line of the fractionating tower T60 is used for extracting oil;
④ Other hydrocarbon oil products of the fractionation column T60.
In the process of regenerating the double-purpose extractant, the circulating double-purpose extractant JY1 of the invention ⑵ can be selected from one or more of the following materials:
① The reflux liquid from the reflux drum at the top of the fractionating tower UT is selected from one or more of the following streams:
Firstly, condensing and cooling tower top gas of a fractionating tower UT, and then entering a tower top reflux tank to separate out tower top reflux tank hydrocarbon oil, wherein at least part of the tower top reflux tank hydrocarbon oil returns to the top of the fractionating tower UT to become tower top reflux liquid RFX1;
at least a part of the tower top reflux liquid RFX1 is used as a circulating type dual-purpose extractant JY1;
Secondly, the tower top gas of the fractionating tower UT generates 2 or more tower top condensate liquid through 2-stage or multi-stage condensation cooling separation process, and any one or more tower top condensate liquid returns to the top of the fractionating tower UT to become tower top reflux liquid RFX2;
At least a part of the tower top reflux liquid RFX2 is used as a circulating type dual-purpose extractant JY1;
Thirdly, condensing and cooling tower top gas of the fractionating tower UT, and then entering a tower top reflux tank to separate out hydrocarbon oil in the tower top reflux tank; the hydrocarbon oil in the tower top reflux tank is subjected to a heating and/or depressurization process, and then is subjected to a separation and fractionation process to obtain a tower top condensate for removing light hydrocarbons; at least a portion of the light hydrocarbon-stripped overhead condensate is used as overhead reflux RFX3 and/or at least a portion of the light hydrocarbon-stripped overhead condensate is used as an effluent product;
at least a part of the tower top reflux liquid RFX3 is used as a circulating type dual-purpose extractant JY1;
② Cold circulating reflux liquid at the top of the fractionating tower UT;
The tower top cold circulation reflux mode refers to collecting liquid UT-L888 from an oil collecting device in the upper section of the fractionating tower UT, then enabling the liquid UT-L888 to leave the fractionating tower UT through a liquid outlet UT-L888-N, cooling the liquid through a cooling process, and returning the liquid to a mass transfer cooling section UT-TNC-01 at the uppermost end of the fractionating tower UT so as to enable at least part of rising hydrocarbon steam to be condensed into liquid; in the fractionating tower UT, a mass transfer cooling section UT-TNC-01 is positioned above a liquid outlet UT-L888-N of liquid UT-L888;
③ Reflux oil from the middle section of the fractionating tower UT;
④ Other hydrocarbon oil products of the fractionation column UT.
In general, the density of ⑵ at 20 ℃ of any one of the double-purpose extractants JY belongs to one of the following values:
①0.95～0.90g/cm3;②0.90～0.85g/cm3;③0.85～0.80g/cm3;④0.80～0.75g/cm3;
⑤＜0.75g/cm3。
in general, the organic oxygen content of the extracting agent JY used for any path of ⑵ belongs to one of the following values:
①0.70～0.55wt％;②0.55～0.40wt％;③＜0.40wt％。
In the present invention, generally, ⑵ any path of the extractant JY is used as the distillation range of ASTM D-86, the temperature of the distillation point is 5wt% to 95wt%, and the temperature belongs to one of the following values:
①80～130℃;②80～150℃;③80～170℃;④120～180℃;⑤130～180℃；
⑥140～180℃;⑦180～230℃;⑧190～230℃;⑨200～230℃;⑩210～260℃；
220～260℃；/>230～260℃；/>150～260℃；/>160～250℃；/>170～230℃。
in the present invention, generally, ⑴ in the extraction process E100, the ratio of the operation volume flow rate of the extractant JY-X to the operation volume flow rate of the sewage F10-X is the agent/water volume ratio K100 in the extraction process, and the value of the agent/water volume ratio K100 is one of the following values:
①10.0～5.0;②5.0～2.0;③2.0～1.0;④1.0～0.50；
⑤0.50～0.10;⑥0.10～0.01。
In general, the operating temperature of ⑴ extraction process E100 of the present invention is selected from one of the following data:
①10～20℃;②20～30℃;③30～40℃;④40～50℃;⑤50～60℃;⑥60～80℃。
In general, the operating pressure of ⑴ extraction process E100 according to the present invention is selected from one of the following data:
①0.0～0.1MPaG;②0.1～0.2MPaG;③0.2～0.3MPaG;④0.3～1.0MPaG。
In general, the operating objective of ⑴ extraction process E100 according to the present invention is expressed as the ratio of the weight concentration of hydrocarbon oil of de-oiled water F10P-X to the weight concentration of hydrocarbon oil of sewage F10-X, selected from one of the following data:
① 0.90 to 0.80 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 10 to 20 weight percent;
② 0.80 to 0.70 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 20 to 30 weight percent;
③ 0.70 to 0.60 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 30 to 40 weight percent;
④ 0.60 to 0.50 percent, namely, the removal rate of hydrocarbon oil in the sewage F10-X is 40 to 50 weight percent;
⑤ 0.50 to 0.40 percent, namely, the removal rate of hydrocarbon oil in the sewage F10-X is 50 to 60 weight percent;
⑥ 0.40 to 0.30 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 60 to 70 percent by weight;
⑦ 0.30 to 0.20 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 70 to 80 weight percent;
⑧ The removal rate of hydrocarbon oil in the sewage F10-X is more than 80wt percent.
In general, the aim of the present invention, ⑴ extraction process E100, is to select from one of the following data the ratio of the weight concentration of hydrocarbon oils with a conventional boiling point higher than 150℃for de-oiled water F10P-X to the weight concentration of hydrocarbon oils with a conventional boiling point higher than 150℃for sewage F10-X:
① 0.90 to 0.80 percent, namely the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is 10 to 20 weight percent;
② 0.80 to 0.70 percent, namely the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is 20 to 30 weight percent;
③ 0.70 to 0.60, namely, the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is 30 to 40 weight percent;
④ 0.60 to 0.50 percent, namely, the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is 40 to 50 percent by weight;
⑤ 0.50 to 0.40 percent, namely, the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is 50 to 60 weight percent;
⑥ 0.40 to 0.30 percent, namely the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is 60 to 70 percent by weight;
⑦ 0.30 to 0.20, namely, the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is 70 to 80 weight percent;
⑧ The removal rate of hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is less than 0.20 and is more than 80 weight percent.
In general, the aim of the present invention, ⑴ extraction process E100, is to select the ratio of the weight concentration of phenol of the de-oiled water F10P-X to the weight concentration of phenol of the sewage F10-X, from one of the following data:
① 0.90 to 0.80 percent, namely the removal rate of phenol in the sewage F10-X is 10 to 20 weight percent;
② 0.80 to 0.70 percent, namely the removal rate of phenol in the sewage F10-X is 20 to 30 weight percent;
③ 0.70 to 0.60, namely, the removal rate of phenol in the sewage F10-X is 30 to 40 weight percent;
④ 0.60 to 0.50 percent, namely the removal rate of phenol in the sewage F10-X is 40 to 50 percent by weight;
⑤ 0.50 to 0.40 percent, namely 50 to 60 percent of phenol in the sewage F10-X;
⑥ The removal rate of phenol in sewage F10-X is more than 60wt percent.
In the present invention, generally, ⑶ in the supplemental extraction process E200, the hydrocarbon oil containing the dual-purpose extractant JY in the primary purified water is extracted with the supplemental extractant 2PY with high hydrogen saturation;
in the supplementary extraction process E200, the sewage F20-X based on primary purified water and the extractant based on the supplementary extractant 2PY are mixed and contacted at least once to become a mixed stream E200-XM, and the mixed stream E200-XM is separated into the supplementary extractant 2PYP-X and the deoiled water F20P-X;
the operation density of the supplementary extractant 2PY is lower than that of the sewage F20-X;
the weight flow rate of hydrocarbons in the rich supplemental extractant 2PYP-X is higher than the weight flow rate of hydrocarbons in the supplemental extractant 2 PY;
the weight concentration of hydrocarbon oil in the deoiling water F20P-X is lower than that in the primary purified water sewage F20-X.
In general, the present invention, ⑷, is rich in the supplemental extractant 2PYP-X, in one or more of the following ways:
① Entering a coal hydrogenation direct liquefaction reaction process R10;
② The separation and fractionation process of the generated oil in the coal hydrogenation direct liquefaction reaction process R10 are carried out;
③ Entering a hydrogen-supplying solvent hydrogenation stabilization reaction process R20 for processing a hydrocarbon stream which is based on the oil generated by the coal hydrogenation direct liquefaction reaction process R10;
④ The separation and fractionation process of the generated oil of the hydrogen-supplying solvent hydrogenation stabilization reaction process R20 for processing the hydrocarbon stream based on the oil generated in the coal hydrogenation direct liquefaction reaction process R10;
⑤ Entering into fractionating tower UT;
⑥ Entering a hydro-upgrading reaction process R30 for processing a hydrocarbon stream which is based on the oil generated by the coal hydrogenation direct liquefaction reaction process R10;
⑦ A hydro-upgrading reaction process R30 for processing the hydrocarbon stream of the generated oil of the hydrogen-supplying solvent hydro-stabilization reaction process R20 based on the hydrocarbon stream of the generated oil of the coal hydrogenation direct liquefaction reaction process R10;
⑧ As absorption oil, the oil enters an absorption process of the rich gas to remove the liquefied gas component;
⑨ The absorption oil which is taken as absorption oil enters the absorption process of the rich gas and liquefied gas removal component is converted into rich absorption oil, and the rich absorption oil enters the hydrogenation reaction process.
In the present invention, ⑶ is a separation and fractionation process of the produced oil from the hydro-upgrading reaction process R30 in the supplemental extraction process E200 using the supplemental extractant 2 PY;
Hydrocarbon stream based on oil generated in the coal hydrogenation direct liquefaction reaction process R10 enters the hydro-upgrading reaction process R30, or
The hydrocarbon stream of the generated oil of the hydrogen supply solvent hydrogenation stabilization reaction process R20 based on the hydrocarbon stream of the generated oil of the coal hydrogenation direct liquefaction reaction process R10 enters the hydro-upgrading reaction process R30.
In the invention, ⑶ is generally used in the supplementary extraction process E200, and the density of the supplementary extracting agent 2PY at 20 ℃ is less than 0.80g/cm 3;
The dry point of the ASTM D-86 distillation range of the supplemental extractant 2PY is less than 180 ℃;
the organic oxygen content of the supplemental extractant 2PY is less than 0.05wt%;
the ratio of the operating volume flow rate of the supplemental extractant 2PY to the operating volume flow rate of the primary purified water is the agent/water volume ratio K200 of the supplemental extraction process, K200 being one of the following values:
①0.30～0.20;②0.20～0.10;③0.10～0.01；
The operation temperature of the supplementary extraction process E200 is 20-60 ℃;
the operating pressure of the supplementary extraction process E200 is 0.0 to 0.3MPaG.
In general, the aim of the operations of the ⑶ -up extraction process E200 according to the present invention is that the ratio of the weight concentration of hydrocarbon oil in the de-oiled water P20-X to the weight concentration of hydrocarbon oil in the primary purified water is selected from one of the following data:
① 0.90 to 0.80 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 10 to 20 weight percent;
② 0.80 to 0.70 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 20 to 30 weight percent;
③ 0.70 to 0.60 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 30 to 40 weight percent;
④ 0.60 to 0.50 percent, namely, the removal rate of hydrocarbon oil in the sewage F10-X is 40 to 50 weight percent;
⑤ 0.50 to 0.40 percent, namely, the removal rate of hydrocarbon oil in the sewage F10-X is 50 to 60 weight percent;
⑥ The removal rate of hydrocarbon oil in sewage F10-X is less than 0.40 and is more than 60 weight percent.
In general, the aim of the operation of the ⑶ -up extraction process E200 according to the present invention is that the ratio of the weight concentration of hydrocarbon oils with a conventional boiling point of the de-oiled water P20-X higher than 150℃to the weight concentration of hydrocarbon oils with a conventional boiling point of the primary purified water higher than 150℃is selected from one of the following data:
① Is 0.90 to 0.80, namely the removal rate of hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the primary purified water is 10 to 20 weight percent;
② Is 0.80 to 0.70, namely the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the primary purified water is 20 to 30 weight percent;
③ 0.70 to 0.60, namely, the removal rate of hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the primary purified water is 30 to 40 weight percent;
④ The removal rate of the hydrocarbon oil in the primary purified water is 0.60 to 0.50 percent, namely, the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the primary purified water is 40 to 50 percent by weight;
⑤ The removal rate of hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the primary purified water is more than 50wt percent, which is less than 0.50-0.40.
In the present invention, in general, a demulsifier mainly composed of carbon and hydrogen that can be converted by hydrogenation reaction is used in the extraction process E100 or the supplementary extraction process E200;
The demulsifier is used for breaking emulsified oil-water mixed liquid drops, so that at least partial separation of oil and water phases in the emulsified oil-water mixed liquid drops occurs, the demulsified and separated oil phase enters a main oil phase product of the extraction process E100 or the supplementary extraction process E200, and the demulsified and separated water phases enter a main water phase product of the extraction process E100 or the supplementary extraction process E200.
In the present invention, in general, in the extraction process E100 or the supplementary extraction process E200, there are at least 2 extraction stages using different extraction agents operated in series, and the main flow of the sewage is taken as the advancing direction, and the properties of the extraction agent used in the downstream extraction stage are 1 or several of the following characteristics compared with those of the extraction agent used in the upstream extraction stage;
① The density of the extractant used in the downstream extraction stage is lower than that of the extractant used in the upstream extraction stage;
② The dry point of the ASTM D-86 distillation range of the extractant used in the downstream extraction stage is lower than the dry point of the ASTM D-86 distillation range of the extractant used in the upstream extraction stage;
③ The organic oxygen content of the extractant used in the downstream extraction stage is lower than that of the extractant used in the upstream extraction stage;
④ The aromatic hydrocarbon content of the extractant used in the downstream extraction section is lower than that of the extractant used in the upstream extraction section;
⑤ The downstream extraction stage uses an extractant having a higher hydrogen content than the upstream extraction stage.
In general, according to the invention, at least one extraction stage is present in the extraction process E100 or in the supplemental extraction process E200;
the operation mode of the extraction section is selected from one or more of the following operation modes:
① One extraction section comprises single contact and single separation, raw material water EFW-X and raw material extractant EFY-X are mixed and contacted to form a mixed flow EMS-X, and the mixed flow EMS-X is separated into extractant-rich EPY-X and de-oiled water EPW-X;
the mixing and contacting process of the dehydrated water EPW-X and the raw material extractant EFY-X uses a mixer to forcedly mix;
the EMS-X separation mode of the mixture flow is selected from one or more of sedimentation separation and centrifugal separation;
② One extraction section comprises 2 countercurrent contacts and 2 separations, and raw water EFW-X and raw extractant EFY-X are in countercurrent mixed contact for 2 times;
In the first contact separation step, raw water EFW-X is mixed and contacted with a first intermediate extraction-rich agent EPY-X1 discharged in the second contact separation step to form a mixed flow EMS-X1, and the mixed flow EMS-X1 is separated into a second extraction-rich agent EPY-X2 and a first deoiling water EPW-X1;
In the second contact separation step, the first dehydrated water EPW-X1 is mixed and contacted with the raw material extractant EFY-X to form a mixed stream EMS-X2, and the mixed stream EMS-X2 is separated into a first extractant-rich EPY-X1 and a second dehydrated water EPW-X2;
③ One extraction section comprises 3 countercurrent contacts and 3 separations, and raw water EFW-X and raw extractant EFY-X are in countercurrent mixed contact for 3 times;
In the first contact separation step, raw water EFW-X and a second intermediate extraction-rich agent EPY-X2 discharged in the second contact separation step are mixed and contacted to form a mixed flow EMS-X1, and the mixed flow EMS-X1 is separated into a third extraction-rich agent EPY-X3 and a first deoiling water EPW-X1;
In the second contact separation step, the first oil removal water EPW-X1 is mixed and contacted with the first intermediate extraction agent EPY-X1 discharged in the third contact separation step to form a mixed flow EMS-X2, and the mixed flow EMS-X2 is separated into a second extraction agent EPY-X2 and a second oil removal water EPW-X2;
In the third contact separation step, the second dehydrated water EPW-X2 is mixed and contacted with the raw material extractant EFY-X to form a mixed stream EMS-X3, and the mixed stream EMS-X3 is separated into a first extractant-rich EPY-X1 and a third dehydrated water EPW-X3;
④ One extraction section comprises more than 3 times of countercurrent contact of sewage and an extractant and more than 3 times of oil-water separation;
⑤ Static internal extraction tower
The extraction process uses an extraction tower of a static tower internal part, and sewage and an extractant are subjected to countercurrent contact separation for a plurality of times;
When the volume flow rate of the extractant is larger than the volume flow rate of the sewage, the extractant is used as a continuous phase, the sewage is dispersed by the distributor and then used as a dispersed phase, and the sewage is dispersed by the distributor to increase the particle number of sewage liquid drops and reduce the diameter of sewage particles;
mass transfer elements of static extraction columns using trays and/or packing;
Static extraction towers, the number of trays is usually 3-100, and typically 40-60;
when the static extraction tower uses the filler, the filler is distributed in multiple layers, and redistributor internals are arranged between the filler layers to redistribute the descending water phase and the ascending extractant oil phase;
⑥ Dynamic internal extraction tower
The extraction process uses an extraction tower of dynamic tower internals, and the extraction tower of the dynamic tower internals uses a turntable or other dynamic tower internals;
when the inner rotary table is used in the dynamic column inner extraction column, the rotary table serves as a stirrer, and is a flat-disc rotary table or other rotary tables;
When the volume flow rate of the extractant is larger than the volume flow rate of the sewage, the extractant is used as a continuous phase, the sewage is dispersed by the distributor and then used as a dispersed phase, and the sewage is dispersed by the distributor to increase the particle number of sewage liquid drops and reduce the diameter of sewage particles;
extraction columns for dynamic column internals, with or without stationary trays and/or packing layers;
when the inner tower rotating disc is used in the extraction tower of the dynamic tower internals, the number of the inner tower rotating disc is usually 3-100, and is usually 40-60;
When the packing is used in the extraction tower of the dynamic tower internals, the packing is distributed in a plurality of layers, and redistributing internals are arranged among the packing layers to redistribute the descending water phase and the ascending extractant oil phase;
the rotation speed of the turntable is usually 10 to 60 rpm, and is usually 20 to 40 rpm.
In the present invention, at least one extraction mass transfer section using an extraction column, which is a rotating disc type extraction column, is generally present in the extraction process E100 or the supplementary extraction process E200, and the number of rotatable trays of the mass transfer section of the rotating disc type extraction column is 20 to 100.
Claims (25)
1. The method for extracting aromatic hydrocarbon in sewage by using the dual-purpose extractant is characterized by comprising the following steps of:
sewage F10, which contains aromatic hydrocarbon and phenol or not;
the extractant JY is used as the extractant with different compositions of 1 path or 2 paths or multiple paths of hydrocarbon;
⑴ In the extraction process E100, sewage F10-X based on sewage F10 and a dual-purpose extractant JY-X based on the dual-purpose extractant JY are mixed and contacted for at least one time to form a mixture flow E100-XM, and the mixture flow E100-XM is separated into a dual-purpose rich extractant RJY-X and de-oiled water F10P-X; the deoiled water product discharged from the extraction process E100 is used as primary purified water; the extraction process E100 discharges a rich and dual-purpose extractant product;
In the extraction process E100, the operation density of the extractant JY-X is lower than that of the sewage F10-X;
The weight flow rate of the hydrocarbon in the rich dual-purpose extractant RJY-X is higher than the weight flow rate of the hydrocarbon in the dual-purpose extractant JY-X;
The weight concentration of the hydrocarbon oil of the deoiling water F10P-X is lower than that of the hydrocarbon oil of the sewage F10-X;
The extracted wastewater finally leaving the extraction process E100 is used as primary purified water;
⑵ Treatment of Fu-dual purpose extractant RJY-X
The treatment of the rich and dual-purpose extractant RJY-X selects 1 or more of the following operation modes:
① Based on hydrocarbon material flow rich in the dual-purpose extractant RJY-X, the hydrocarbon material flow enters a fractionating tower UT for simultaneously processing other hydrocarbon material flows S10 to separate out the dual-purpose extractant JY for recycling, and the dual-purpose extractant JY belongs to the recycling dual-purpose extractant JY1;
a fractionation column UT separating 2 and or more narrow-cut hydrocarbon oils;
② Based on the hydrocarbon stream rich in the dual-purpose extractant RJY-X, entering a hydrogenation reaction process and/or entering a fractionation process U55 for simultaneously processing other hydrocarbon streams S55, wherein the fractionation process U55 does not produce the dual-purpose extractant JY, and the dual-purpose extractant JY belongs to the single-way dual-purpose extractant JY2;
the fractionation column UT55 of the fractionation process U55 separates 2 and or more narrow-cut hydrocarbon oils.
2. The method according to claim 1, wherein:
the weight flow rate of phenol in rich dual-purpose extractant RJY-X is higher than that in dual-purpose extractant JY-X;
The weight concentration of phenol in the deoiling water F10P-X is lower than that in the sewage F10-X.
3. The method according to claim 1, wherein:
⑵ In the process of regenerating the dual-purpose extractant, a fractionating tower UT system is used;
A hydrocarbon stream based on oil generated in the coal hydrogenation direct liquefaction reaction process R10 is converted into a reaction effluent R20P in the hydrogenation stabilization reaction process R20 for producing hydrogen-donating solvent, and the hydrogenation stabilization reaction generated oil R20PY is obtained based on the reaction effluent R20P;
At least a portion of the hydrocarbon stream based on the hydrostabilization reaction to form oil R20PY is fed to fractionation column UT for distillative separation and at least 2 different fractions of hydrocarbon oil are separated.
4. A method according to claim 1 or 2 or 3, characterized in that:
Sewage F10, selected from one or several of the following streams:
① Cold high-molecular acid water in the coal hydrogenation direct liquefaction process;
② Cold low-pressure acidic water in the coal hydrogenation direct liquefaction process;
③ The coal hydrogenation direct liquefaction process generates sewage of the fractionation process of oil;
④ Cold high-molecular acid water of solvent oil hydrogenation stabilizing device matched with coal hydrogenation direct liquefying device;
⑤ Cold low-fraction acidic water of a solvent oil hydrogenation stabilizing device matched with a coal hydrogenation direct liquefying device;
⑥ The tower top sewage of the coal tar fractionating tower;
⑦ Sewage generated in the coal gasification process;
⑧ Other aromatic hydrocarbon-containing and phenol-containing sewage.
5. The method according to claim 1, wherein:
⑵ Single-pass type dual-purpose extractant JY2 source
Single pass dual purpose extractant JY2 is a narrow fraction, low molecular weight hydrocarbon stream from the hydrocarbon fractionation column T60 system;
fractionation column T60 of the hydrocarbonaceous material is not fractionation column UT55 nor UT of fractionation process U55;
single-pass dual-purpose extractant JY2 is selected from one or more of the following streams:
① The product of the top reflux drum of the fractionating tower T60 is selected from any one or more of the following:
Firstly, condensing and cooling tower top gas of a fractionating tower T60, and then entering a tower top reflux tank to separate out tower top reflux tank hydrocarbon oil, wherein at least a part of the tower top reflux tank hydrocarbon oil is used as a single-pass dual-purpose extractant JY2;
Secondly, the tower top gas of the fractionating tower T60 is subjected to 2-stage or multi-stage condensation, cooling and separation processes to generate 2 or more tower top condensate, and any one or more tower top condensate is/are used as a single-pass dual-purpose extractant JY2;
Thirdly, condensing and cooling the tower top gas of the fractionating tower T60, and then entering a tower top reflux tank to separate out hydrocarbon oil in the tower top reflux tank; at least one part of the light hydrocarbon-removed liquid obtained by heating and/or depressurizing hydrocarbon oil in the tower top reflux tank and then separating and fractionating is used as a single-pass dual-purpose extractant JY2;
② The top side draw of the fractionation column T60;
③ The middle side line of the fractionating tower T60 is used for extracting oil;
④ Other hydrocarbon oil products of the fractionation column T60.
6. The method according to claim 1, wherein:
⑵ In the process of regenerating the dual-purpose extractant, the circulating dual-purpose extractant JY1 is selected from one or more of the following materials:
① The reflux liquid from the reflux drum at the top of the fractionating tower UT is selected from one or more of the following streams:
Firstly, condensing and cooling tower top gas of a fractionating tower UT, and then entering a tower top reflux tank to separate out tower top reflux tank hydrocarbon oil, wherein at least part of the tower top reflux tank hydrocarbon oil returns to the top of the fractionating tower UT to become tower top reflux liquid RFX1;
at least a part of the tower top reflux liquid RFX1 is used as a circulating type dual-purpose extractant JY1;
Secondly, the tower top gas of the fractionating tower UT generates 2 or more tower top condensate liquid through 2-stage or multi-stage condensation cooling separation process, and any one or more tower top condensate liquid returns to the top of the fractionating tower UT to become tower top reflux liquid RFX2;
At least a part of the tower top reflux liquid RFX2 is used as a circulating type dual-purpose extractant JY1;
Thirdly, condensing and cooling tower top gas of the fractionating tower UT, and then entering a tower top reflux tank to separate out hydrocarbon oil in the tower top reflux tank; the hydrocarbon oil in the tower top reflux tank is subjected to a heating and/or depressurization process, and then is subjected to a separation and fractionation process to obtain a tower top condensate for removing light hydrocarbons; at least a portion of the light hydrocarbon-stripped overhead condensate is used as overhead reflux RFX3 and/or at least a portion of the light hydrocarbon-stripped overhead condensate is used as an effluent product;
at least a part of the tower top reflux liquid RFX3 is used as a circulating type dual-purpose extractant JY1;
② Cold circulating reflux liquid at the top of the fractionating tower UT;
The tower top cold circulation reflux mode refers to collecting liquid UT-L888 from an oil collecting device in the upper section of the fractionating tower UT, then enabling the liquid UT-L888 to leave the fractionating tower UT through a liquid outlet UT-L888-N, cooling the liquid through a cooling process, and returning the liquid to a mass transfer cooling section UT-TNC-01 at the uppermost end of the fractionating tower UT so as to enable at least part of rising hydrocarbon steam to be condensed into liquid; in the fractionating tower UT, a mass transfer cooling section UT-TNC-01 is positioned above a liquid outlet UT-L888-N of liquid UT-L888;
③ Reflux oil from the middle section of the fractionating tower UT;
④ Other hydrocarbon oil products of the fractionation column UT.
7. The method according to claim 1, wherein:
⑵ The density of any path of the extractant JY at 20 ℃ belongs to one of the following values:
①0.95～0.90g/cm3;②0.90～0.85g/cm3;③0.85～0.80g/cm3;④0.80～0.75g/cm3;
⑤＜0.75g/cm3。
8. The method according to claim 1, wherein:
⑵ The organic oxygen content of any path of the dual-purpose extractant JY belongs to one of the following values:
①0.70～0.55wt％;②0.55～0.40wt％;③＜0.40wt％。
9. The method according to claim 1, wherein:
⑵ Any one of the two-purpose extractant JY with the temperature of 5wt% of the distillation range of ASTM D-86 to 95wt% of the distillation point belongs to one of the following values:
①80～130℃;②80～150℃;③80～170℃;④120～180℃;⑤130～180℃；
⑥140～180℃;⑦180～230℃;⑧190～230℃;⑨200～230℃;⑩210～260℃；
220～260℃；/>230～260℃；/>150～260℃；/>160～250℃；/>170～230℃。
10. The method according to claim 1, wherein:
⑴ In the extraction process E100, the ratio of the operation volume flow rate of the extractant JY-X to the operation volume flow rate of the sewage F10-X is the agent/water volume ratio K100 in the extraction process, and the agent/water volume ratio K100 takes one of the following values:
①10.0～5.0;②5.0～2.0;③2.0～1.0;④1.0～0.50；
⑤0.50～0.10;⑥0.10～0.01。
11. the method according to claim 1, wherein:
⑴ The operating temperature of extraction process E100 is selected from one of the following data:
①10～20℃;②20～30℃;③30～40℃;④40～50℃;⑤50～60℃;⑥60～80℃。
12. the method according to claim 1, wherein:
⑴ The operating pressure of extraction process E100 is selected from one of the following data:
①0.0～0.1MPaG;②0.1～0.2MPaG;③0.2～0.3MPaG;④0.3～1.0MPaG。
13. the method according to claim 1, wherein:
⑴ The operating objective of the extraction process E100, expressed as the ratio of the weight concentration of hydrocarbon oil of the deoiled water F10P-X to the weight concentration of hydrocarbon oil of the sewage F10-X, is selected from one of the following data:
① 0.90 to 0.80 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 10 to 20 weight percent;
② 0.80 to 0.70 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 20 to 30 weight percent;
③ 0.70 to 0.60 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 30 to 40 weight percent;
④ 0.60 to 0.50 percent, namely, the removal rate of hydrocarbon oil in the sewage F10-X is 40 to 50 weight percent;
⑤ 0.50 to 0.40 percent, namely, the removal rate of hydrocarbon oil in the sewage F10-X is 50 to 60 weight percent;
⑥ 0.40 to 0.30 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 60 to 70 percent by weight;
⑦ 0.30 to 0.20 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 70 to 80 weight percent;
⑧ The removal rate of hydrocarbon oil in the sewage F10-X is more than 80wt percent.
14. The method according to claim 1, wherein:
⑴ The extraction process E100 is operated with the aim that the ratio of the weight concentration of hydrocarbon oil with a conventional boiling point of the de-oiled water F10P-X higher than 150 ℃ to the weight concentration of hydrocarbon oil with a conventional boiling point of the sewage F10-X higher than 150 ℃ is selected from one of the following data:
① 0.90 to 0.80 percent, namely the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is 10 to 20 weight percent;
② 0.80 to 0.70 percent, namely the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is 20 to 30 weight percent;
③ 0.70 to 0.60, namely, the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is 30 to 40 weight percent;
④ 0.60 to 0.50 percent, namely, the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is 40 to 50 percent by weight;
⑤ 0.50 to 0.40 percent, namely, the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is 50 to 60 weight percent;
⑥ 0.40 to 0.30 percent, namely the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is 60 to 70 percent by weight;
⑦ 0.30 to 0.20, namely, the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is 70 to 80 weight percent;
⑧ The removal rate of hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the sewage F10-X is less than 0.20 and is more than 80 weight percent.
15. The method according to claim 1, wherein:
⑴ The extraction process E100 is operated with the aim of providing the ratio of the phenol weight concentration of the de-oiled water F10P-X to the phenol weight concentration of the sewage F10-X, selected from one of the following data:
① 0.90 to 0.80 percent, namely the removal rate of phenol in the sewage F10-X is 10 to 20 weight percent;
② 0.80 to 0.70 percent, namely the removal rate of phenol in the sewage F10-X is 20 to 30 weight percent;
③ 0.70 to 0.60, namely, the removal rate of phenol in the sewage F10-X is 30 to 40 weight percent;
④ 0.60 to 0.50 percent, namely the removal rate of phenol in the sewage F10-X is 40 to 50 percent by weight;
⑤ 0.50 to 0.40 percent, namely 50 to 60 percent of phenol in the sewage F10-X;
⑥ The removal rate of phenol in sewage F10-X is more than 60wt percent.
16. The method according to claim 1, wherein:
⑶ In the supplementary extraction process E200, the hydrocarbon oil containing the double-purpose extractant JY in the primary purified water is extracted by using the supplementary extractant 2PY with high hydrogen saturation;
in the supplementary extraction process E200, the sewage F20-X based on primary purified water and the extractant based on the supplementary extractant 2PY are mixed and contacted at least once to become a mixed stream E200-XM, and the mixed stream E200-XM is separated into the supplementary extractant 2PYP-X and the deoiled water F20P-X;
the operation density of the supplementary extractant 2PY is lower than that of the sewage F20-X;
the weight flow rate of hydrocarbons in the rich supplemental extractant 2PYP-X is higher than the weight flow rate of hydrocarbons in the supplemental extractant 2 PY;
the weight concentration of hydrocarbon oil in the deoiling water F20P-X is lower than that in the primary purified water sewage F20-X.
17. The method according to claim 16, wherein:
⑷ The rich supplemental extractant 2PYP-X is sent to one or more of the following modes:
① Entering a coal hydrogenation direct liquefaction reaction process R10;
② The separation and fractionation process of the generated oil in the coal hydrogenation direct liquefaction reaction process R10 are carried out;
③ Entering a hydrogen-supplying solvent hydrogenation stabilization reaction process R20 for processing a hydrocarbon stream which is based on the oil generated by the coal hydrogenation direct liquefaction reaction process R10;
④ The separation and fractionation process of the generated oil of the hydrogen-supplying solvent hydrogenation stabilization reaction process R20 for processing the hydrocarbon stream based on the oil generated in the coal hydrogenation direct liquefaction reaction process R10;
⑤ Entering into fractionating tower UT;
⑥ Entering a hydro-upgrading reaction process R30 for processing a hydrocarbon stream which is based on the oil generated by the coal hydrogenation direct liquefaction reaction process R10;
⑦ A hydro-upgrading reaction process R30 for processing the hydrocarbon stream of the generated oil of the hydrogen-supplying solvent hydro-stabilization reaction process R20 based on the hydrocarbon stream of the generated oil of the coal hydrogenation direct liquefaction reaction process R10;
⑧ As absorption oil, the oil enters an absorption process of the rich gas to remove the liquefied gas component;
⑨ The absorption oil which is taken as absorption oil enters the absorption process of the rich gas and liquefied gas removal component is converted into rich absorption oil, and the rich absorption oil enters the hydrogenation reaction process.
18. The method according to claim 16, wherein:
⑶ In the supplemental extraction process E200, the supplemental extractant 2PY used is a separation and fractionation process of the produced oil from the hydro-upgrading reaction process R30;
Hydrocarbon stream based on oil generated in the coal hydrogenation direct liquefaction reaction process R10 enters the hydro-upgrading reaction process R30, or
The hydrocarbon stream of the generated oil of the hydrogen supply solvent hydrogenation stabilization reaction process R20 based on the hydrocarbon stream of the generated oil of the coal hydrogenation direct liquefaction reaction process R10 enters the hydro-upgrading reaction process R30.
19. The method according to claim 16, wherein:
⑶ In the supplementary extraction process E200, the density of the supplementary extracting agent 2PY at 20 ℃ is less than 0.80g/cm 3;
The dry point of the ASTM D-86 distillation range of the supplemental extractant 2PY is less than 180 ℃;
the organic oxygen content of the supplemental extractant 2PY is less than 0.05wt%;
the ratio of the operating volume flow rate of the supplemental extractant 2PY to the operating volume flow rate of the primary purified water is the agent/water volume ratio K200 of the supplemental extraction process, K200 being one of the following values:
①0.30～0.20;②0.20～0.10;③0.10～0.01；
The operation temperature of the supplementary extraction process E200 is 20-60 ℃;
the operating pressure of the supplementary extraction process E200 is 0.0 to 0.3MPaG.
20. The method according to claim 16, wherein:
⑶ The supplemental extraction process E200 operates with the objective that the ratio of the weight concentration of hydrocarbon oil in the de-oiled water P20-X to the weight concentration of hydrocarbon oil in the primary purified water be selected from one of the following data:
① 0.90 to 0.80 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 10 to 20 weight percent;
② 0.80 to 0.70 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 20 to 30 weight percent;
③ 0.70 to 0.60 percent, namely the removal rate of hydrocarbon oil in the sewage F10-X is 30 to 40 weight percent;
④ 0.60 to 0.50 percent, namely, the removal rate of hydrocarbon oil in the sewage F10-X is 40 to 50 weight percent;
⑤ 0.50 to 0.40 percent, namely, the removal rate of hydrocarbon oil in the sewage F10-X is 50 to 60 weight percent;
⑥ The removal rate of hydrocarbon oil in sewage F10-X is less than 0.40 and is more than 60 weight percent.
21. The method according to claim 16, wherein:
⑶ The supplemental extraction process E200 is operated with the aim that the ratio of the weight concentration of hydrocarbon oil with a conventional boiling point of the de-oiled water P20-X higher than 150 ℃ to the weight concentration of hydrocarbon oil with a conventional boiling point higher than 150 ℃ in the primary purified water is selected from one of the following data:
① Is 0.90 to 0.80, namely the removal rate of hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the primary purified water is 10 to 20 weight percent;
② Is 0.80 to 0.70, namely the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the primary purified water is 20 to 30 weight percent;
③ 0.70 to 0.60, namely, the removal rate of hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the primary purified water is 30 to 40 weight percent;
④ The removal rate of the hydrocarbon oil in the primary purified water is 0.60 to 0.50 percent, namely, the removal rate of the hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the primary purified water is 40 to 50 percent by weight;
⑤ The removal rate of hydrocarbon oil with the conventional boiling point higher than 150 ℃ in the primary purified water is more than 50wt percent, which is less than 0.50-0.40.
22. The method according to claim 1 or 16, characterized in that:
In the extraction process E100 or the supplementary extraction process E200, demulsifiers which are mainly composed of carbon elements and hydrogen elements and can be converted by hydrogenation reaction are used;
The demulsifier is used for breaking emulsified oil-water mixed liquid drops, so that at least partial separation of oil and water phases in the emulsified oil-water mixed liquid drops occurs, the demulsified and separated oil phase enters a main oil phase product of the extraction process E100 or the supplementary extraction process E200, and the demulsified and separated water phases enter a main water phase product of the extraction process E100 or the supplementary extraction process E200.
23. The method according to claim 1 or 16, characterized in that:
In the extraction process E100 or the supplementary extraction process E200, at least 2 extraction sections which are operated in series and use different extraction agents are arranged, the main flow of sewage is taken as the advancing direction, and the properties of the extraction agents used in the downstream extraction section are compared with those of the extraction agents used in the upstream extraction section, and the extraction sections have 1 or more of the following characteristics;
① The density of the extractant used in the downstream extraction stage is lower than that of the extractant used in the upstream extraction stage;
② The dry point of the ASTM D-86 distillation range of the extractant used in the downstream extraction stage is lower than the dry point of the ASTM D-86 distillation range of the extractant used in the upstream extraction stage;
③ The organic oxygen content of the extractant used in the downstream extraction stage is lower than that of the extractant used in the upstream extraction stage;
④ The aromatic hydrocarbon content of the extractant used in the downstream extraction section is lower than that of the extractant used in the upstream extraction section;
⑤ The downstream extraction stage uses an extractant having a higher hydrogen content than the upstream extraction stage.
24. The method according to claim 1 or 16 or 23, characterized in that:
At least one extraction stage is present in the extraction process E100 or the supplemental extraction process E200;
the operation mode of the extraction section is selected from one or more of the following operation modes:
① One extraction section comprises single contact and single separation, raw material water EFW-X and raw material extractant EFY-X are mixed and contacted to form a mixed flow EMS-X, and the mixed flow EMS-X is separated into extractant-rich EPY-X and de-oiled water EPW-X;
the mixing and contacting process of the dehydrated water EPW-X and the raw material extractant EFY-X uses a mixer to forcedly mix;
the EMS-X separation mode of the mixture flow is selected from one or more of sedimentation separation and centrifugal separation;
② One extraction section comprises 2 countercurrent contacts and 2 separations, and raw water EFW-X and raw extractant EFY-X are in countercurrent mixed contact for 2 times;
In the first contact separation step, raw water EFW-X is mixed and contacted with a first intermediate extraction-rich agent EPY-X1 discharged in the second contact separation step to form a mixed flow EMS-X1, and the mixed flow EMS-X1 is separated into a second extraction-rich agent EPY-X2 and a first deoiling water EPW-X1;
In the second contact separation step, the first dehydrated water EPW-X1 is mixed and contacted with the raw material extractant EFY-X to form a mixed stream EMS-X2, and the mixed stream EMS-X2 is separated into a first extractant-rich EPY-X1 and a second dehydrated water EPW-X2;
③ One extraction section comprises 3 countercurrent contacts and 3 separations, and raw water EFW-X and raw extractant EFY-X are in countercurrent mixed contact for 3 times;
In the first contact separation step, raw water EFW-X and a second intermediate extraction-rich agent EPY-X2 discharged in the second contact separation step are mixed and contacted to form a mixed flow EMS-X1, and the mixed flow EMS-X1 is separated into a third extraction-rich agent EPY-X3 and a first deoiling water EPW-X1;
In the second contact separation step, the first oil removal water EPW-X1 is mixed and contacted with the first intermediate extraction agent EPY-X1 discharged in the third contact separation step to form a mixed flow EMS-X2, and the mixed flow EMS-X2 is separated into a second extraction agent EPY-X2 and a second oil removal water EPW-X2;
In the third contact separation step, the second dehydrated water EPW-X2 is mixed and contacted with the raw material extractant EFY-X to form a mixed stream EMS-X3, and the mixed stream EMS-X3 is separated into a first extractant-rich EPY-X1 and a third dehydrated water EPW-X3;
④ One extraction section comprises more than 3 times of countercurrent contact of sewage and an extractant and more than 3 times of oil-water separation;
⑤ Static internal extraction tower
The extraction process uses an extraction tower of a static tower internal part, and sewage and an extractant are subjected to countercurrent contact separation for a plurality of times;
When the volume flow rate of the extractant is larger than the volume flow rate of the sewage, the extractant is used as a continuous phase, the sewage is dispersed by the distributor and then used as a dispersed phase, and the sewage is dispersed by the distributor to increase the particle number of sewage liquid drops and reduce the diameter of sewage particles;
mass transfer elements of static extraction columns using trays and/or packing;
Static extraction towers, the number of trays is usually 3-100, and typically 40-60;
when the static extraction tower uses the filler, the filler is distributed in multiple layers, and redistributor internals are arranged between the filler layers to redistribute the descending water phase and the ascending extractant oil phase;
⑥ Dynamic internal extraction tower
The extraction process uses an extraction tower of dynamic tower internals, and the extraction tower of the dynamic tower internals uses a turntable or other dynamic tower internals;
when the inner rotary table is used in the dynamic column inner extraction column, the rotary table serves as a stirrer, and is a flat-disc rotary table or other rotary tables;
When the volume flow rate of the extractant is larger than the volume flow rate of the sewage, the extractant is used as a continuous phase, the sewage is dispersed by the distributor and then used as a dispersed phase, and the sewage is dispersed by the distributor to increase the particle number of sewage liquid drops and reduce the diameter of sewage particles;
extraction columns for dynamic column internals, with or without stationary trays and/or packing layers;
when the inner tower rotating disc is used in the extraction tower of the dynamic tower internals, the number of the inner tower rotating disc is usually 3-100, and is usually 40-60;
When the packing is used in the extraction tower of the dynamic tower internals, the packing is distributed in a plurality of layers, and redistributing internals are arranged among the packing layers to redistribute the descending water phase and the ascending extractant oil phase;
the rotation speed of the turntable is usually 10 to 60 rpm, and is usually 20 to 40 rpm.
25. The method according to claim 1 or 16 or 23, characterized in that:
in the extraction process E100 or the supplementary extraction process E200, at least one extraction mass transfer section using an extraction tower is arranged, the extraction tower is a rotary disc type extraction tower, and the number of rotatable trays of the mass transfer section of the rotary disc type extraction tower is 20-100.
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