CN110885105A - Oil washing method for acidic water obtained in separation process of hydro-thermal cracking products of hydrocarbon material - Google Patents
Oil washing method for acidic water obtained in separation process of hydro-thermal cracking products of hydrocarbon material Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 457
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 234
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 234
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 187
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 186
- 229910001868 water Inorganic materials 0.000 title claims abstract description 173
- 238000005406 washing Methods 0.000 title claims abstract description 86
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 77
- 239000007789 gas Substances 0.000 claims description 74
- 238000004523 catalytic cracking Methods 0.000 claims description 71
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 60
- 239000002904 solvent Substances 0.000 claims description 60
- 238000010521 absorption reaction Methods 0.000 claims description 55
- 238000004939 coking Methods 0.000 claims description 44
- 238000004821 distillation Methods 0.000 claims description 44
- 238000010438 heat treatment Methods 0.000 claims description 44
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 38
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 38
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 32
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 31
- 229910021529 ammonia Inorganic materials 0.000 claims description 30
- 238000009835 boiling Methods 0.000 claims description 28
- 239000008213 purified water Substances 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 19
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- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 150000002431 hydrogen Chemical class 0.000 claims description 14
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- 238000011105 stabilization Methods 0.000 claims description 12
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- 125000001741 organic sulfur group Chemical group 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000002199 base oil Substances 0.000 claims description 7
- 238000003912 environmental pollution Methods 0.000 claims description 7
- 125000001477 organic nitrogen group Chemical group 0.000 claims description 7
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- 238000007670 refining Methods 0.000 claims description 7
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 5
- 239000011269 tar Substances 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 4
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
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- 150000003254 radicals Chemical group 0.000 description 3
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- -1 saturated bicyclic aromatic hydrocarbon Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 108090001146 Nuclear Receptor Coactivator 1 Proteins 0.000 description 1
- 102100037223 Nuclear receptor coactivator 1 Human genes 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
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- 239000010692 aromatic oil Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 239000003085 diluting agent Substances 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
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- 238000002203 pretreatment Methods 0.000 description 1
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- 239000001294 propane Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The oil washing method of the acid water obtained in the separation process of the hydro-thermal cracking products of the hydrocarbon material is particularly suitable for the combined use of the hydro-upgrading process WH of an oil product WPY obtained in the oil washing process WP and WP of the acid water W01 in the separation process of RU products in the hydro-thermal cracking reaction process of coal and/or coal tar and/or heavy oil, the hydro-upgrading reaction product WHP in the hydro-upgrading process WH is separated to obtain a hydrocarbon-containing oil stream PYWH, at least one part of WHPY and/or at least one part of WPY are used as extraction oil to extract inferior conventional liquid hydrocarbon in the acid water W01 to obtain extraction oil, the extraction oil WPY is used as raw oil in the hydro-upgrading process WH, the partial deoiling task of the acid water W01 is realized by a simple process, and the oil washing method can be combined with a deoiling method of ZL201610550628.8 gas containing conventional gas hydrocarbon and inferior conventional liquid hydrocarbon to form a series processing combined.
Description
Technical Field
The invention relates to an oil washing method of acid water obtained in the separation process of hydro-thermal cracking products of hydrocarbon materials, which is particularly suitable for the combined use of the hydro-upgrading process WH of oil WPY obtained in the oil washing process WP and WP of acid water W01 in the separation process of the hydro-thermal cracking reaction process RU products of coal andor coal tar pitch andor heavy oil, the hydro-upgrading reaction product WHP in the hydro-upgrading process WH is separated to obtain hydrocarbon-containing oil flow WHPY, at least one part of WHPY andor at least one part of WPY is used for extracting inferior conventional liquid hydrocarbon in the acid water W01 to obtain extraction oil, the extraction oil WPY is used as raw oil in the hydro-upgrading process WH, the partial deoiling task of the acid water W01 is realized by a simple process, and the oil washing method can be combined with a deoiling method of gas containing conventional gas hydrocarbon and inferior conventional liquid hydrocarbon to form a series processing combined process.
Background
The hydrocarbon material refers to liquid and/or solid containing carbon and hydrogen elements, such as oil and/or coal, and the invention is mainly concerned with the treatment process of acid water in the separation process of hydrocarbon material hydrocracking products, so the hydrocarbon material, in particular to the hydrocarbon material containing oxygen elements, can generate water and phenol components in the hydrocarbon material hydrocracking reaction process.
The hydrocracking reaction process RU of the present invention refers to a hydrocracking reaction process of a hydrocarbon material using a hydrocarbon material as a raw material, and includes a reaction of generating a radical fragment by thermal cracking of the hydrocarbon material and/or a hydrogenation stabilization reaction of thermally cracking the radical fragment, and usually simultaneously performs a hydrorefining reaction and/or a catalytic hydrocracking reaction and/or a hydrocracking reaction, and the like.
The hydrocarbon hydrogenation thermal cracking reaction process RU comprises a hydrogenation thermal cracking reaction process of coal andor coal tar pitch andor heavy oil.
The process for directly liquefying the carbon-hydrogen powder by hydrogenation mainly refers to the process for directly liquefying coal by hydrogenation, but can comprise other carbon-hydrogen powder which is combined with pulverized coal for liquefaction and mainly consists of carbon elements and hydrogen elements, such as powder which is prepared from waste plastics, waste rubber and other solids and can be used for liquefaction. Generally, in order to accelerate hydrogen supply speed, inhibit thermal condensation reaction, reduce reaction heat and improve reaction operability, hydrogen supply solvent oil is used in the efficient direct liquefaction process of hydrogenation of hydrocarbon powder.
The heavy oil in the invention refers to heavy hydrocarbon oil mainly composed of hydrocarbons with the conventional boiling point higher than 350 ℃, preferably mainly composed of hydrocarbons with the conventional boiling point higher than 450 ℃, preferably mainly composed of hydrocarbons with the conventional boiling point higher than 530 ℃, particularly preferably inferior heavy oil mainly composed of heavy hydrocarbons with low hydrogen content and rich in aromatic structural units, with the conventional boiling point higher than 530 ℃; for the hydrogenation reaction process of the inferior heavy oil, particularly the hydrogenation thermal cracking reaction process, in order to accelerate the hydrogen supply speed, inhibit the thermal condensation reaction, reduce the reaction heat and improve the reaction operability, the hydrogen supply solvent oil is needed in the high-efficiency hydrogenation reaction process of the inferior heavy oil.
The hydrorefining reaction of the hydrocarbon material can be hydrogenation impurity removal reaction such as hydrogenation demetallization reaction, hydrogenation organic oxygen removal reaction, hydrogenation organic sulfur removal reaction, hydrogenation organic oxygen removal reaction, hydrogenation organic chlorine removal reaction and hydrogenation organic fluorine removal reaction, can be hydrogenation saturation reaction of unsaturated carbon-carbon bond such as olefin hydrogenation saturation reaction, alkyne hydrogenation saturation reaction and aromatic hydrocarbon hydrogenation saturation reaction, and can be one or more of the reactions. The hydro-thermal cracking reaction of the hydrocarbon material and the hydro-stabilization reaction of the thermal cracking free radical fragments always occur concomitantly, and are generally existed in the high-temperature hydro-thermal cracking reaction process of coal and/or heavy oil, such as a coal hydrogenation direct liquefaction reaction process, a hydrogenation reaction process of kerosene co-refining, a heavy oil hydro-thermal cracking reaction process and a heavy oil hydrogenation reaction process.
In the RU product in the above-mentioned hydrocracking reaction process for a hydrocarbon feedstock, 2 or more components of hydrogen sulfide, ammonia, water, phenol are generally contained; in the separation of the RU products in the above-mentioned hydrothermal cracking reaction process of hydrocarbon feedstock, acidic water SPW01 containing 2 or more components of hydrogen sulfide, ammonia, phenol is generally produced, wherein the aquarium component is derived from the RU raw material or the hydrogenation product of oxygen-carrying raw material in the reaction process or washing water supplied from the outside.
In the SPW01 purification process of the acidic water, 1 or 2 or 3 processes of hydrogen sulfide removal, deamination and dephenolization of the acidic water are generally needed to realize the purification to obtain purified water, and the product of 1 or 2 or 3 processes of hydrogen sulfide removal, deamination and dephenolization of the acidic water, namely intermediate semi-purified water or final purified water, can be returned to the separation process of the product RU in the hydrocarbon material hydrocracking reaction process to be used as washing water for recycling.
Taking the separation process of the direct coal hydrogenation liquefaction reaction product as an example, the purification process of the acidic water SPW01, the acidic water usually needs to be subjected to a pretreatment process of deoiling and filtering to remove solid particles, because:
① the naphtha and diesel oil components in the reaction product of direct liquefaction by coal hydrogenation belong to hydrocarbon oil with high aromaticity and have high solubility in water, the naphtha and diesel oil components in the reaction product of direct liquefaction by coal hydrogenation belong to hydrocarbon oil with high phenol content and the solubility of phenol in water is high, most of the oil and phenol dissolved in water enter acid gas in the process of removing hydrogen sulfide from the acid water, and sulfur can be blackened due to incomplete combustion in the process of preparing sulfur from the acid gas;
② the hot high-pressure gas of the reaction product of coal hydrogenation direct liquefaction is entrained with coal dust or coke powder or catalyst particles or colloidal asphaltenes, and these particles are usually particles of adhered colloidal asphaltenes, which can deposit on the bottom of the heat exchanger, the bottom of the tank, the bottom of the tray, the bottom of the tower, the bottom of the reboiler, block the flow channel, affect the process efficiency of the equipment, such as reducing the heat transfer rate of the heat exchanger, reducing the liquid circulation of the tray, reducing the processing capacity, and in severe cases, causing the flow channel to be blocked, and causing the unplanned shutdown of the device.
The main object of the present invention is to propose an economical pretreatment method of acidic water to reduce the amount or concentration of highly aromatic oils and or phenols in the feed of the acidic water in the processes of hydrogen sulfide removal and deamination, and the proposed method is an oil washing method.
The conventional method for eluting phenol from acidic water and oil is to use light distillate oil with high benzene content to extract phenol and hydrocarbon oil with higher boiling point in the acidic water, but needs to use expensive benzene extractant, and needs to construct a regeneration circulation system of the benzene extractant in order to reduce the consumption of the benzene extractant, and the regeneration circulation system has complex flow, large investment and high energy consumption.
In the hydrogenation stabilization process for producing hydrogen-supplying solvent oil from high aromatic hydrocarbon production oil RUPY directly liquefied by coal hydrogenation or the hydrogenation upgrading reaction process HU for producing final hydrogenation upgraded oil product, it is usually necessary to use hydrogenation production oil or hydrogenation production oil distillate thereof as cycle oil to be used as diluent oil or cycle hydrogenated oil of oil product RUPY (for example, for hydrocracking or deep hydrogenation refining), and these cycle hydrocarbon oils are practically ideal free low aromatic hydrocarbon and low phenol content extraction oils in the acid water game process, i.e., they are used in series again to form cycle oil.
The oil washing method of the acid water obtained in the separation process of the hydro-thermal cracking product of the hydrocarbon material ZL201610550628.8 is particularly suitable for the combined use of the hydro-upgrading process HU of the oil product APY obtained in the de-oiling process AP of the gas APG containing the conventional gas hydrocarbon and the inferior conventional liquid hydrocarbon generated in the thermal processing process P01 of coal tar such AS heating distillation, coking, thermal cracking, shallow hydrogenation process and the like, the hydro-upgrading reaction product HUP of the hydro-upgrading process HU is separated to obtain the hydrocarbon-containing oil stream HUPY, at least one part of HUPY and/or at least one part of APY is used AS the absorption oil AS to absorb the inferior conventional liquid hydrocarbon in the gas APG to obtain the rich absorption oil RS, the rich absorption oil is used AS the raw material of the hydro-upgrading process HU of the oil product APY, and the de-oiling purification of the gas APG and the recovery and upgrading of the inferior hydrocarbon are realized by simple.
So far, the basic idea of the invention is presented: the oil washing method of the acid water obtained in the separation process of the hydro-thermal cracking products of the hydrocarbon material is particularly suitable for the combined use of the hydro-upgrading process WH of the acid water W01 obtained in the oil washing process WP using the extraction oil CY and the extracted rich oil WPY obtained in the hydro-upgrading process WP of the RU product separation process in the hydro-thermal cracking reaction process of coal andor coal tar pitch andor heavy oil, the hydro-upgrading reaction product WHP obtained in the hydro-upgrading process WH is separated to obtain a hydrocarbon-containing oil stream WHPY, at least one part of WHPY andor at least one part of WPY is used as an extracting agent to extract the inferior conventional liquid hydrocarbon in the acid water W01 to obtain the extraction oil, and the extracted rich oil WPY is used as the raw oil in, the method realizes the partial deoiling task of the acidic water W01 by a simple flow, and can be combined with a deoiling method of ZL201610550628.8 gas containing conventional gas hydrocarbon and inferior conventional liquid hydrocarbon to form a series processing combined process.
Taking the purification process of the acidic water SPW01 in the separation process of the coal hydrogenation direct liquefaction reaction product as an example, the hydrogen supply solvent oil produced in the hydrogenation stabilization process of the high aromatic hydrocarbon produced oil RUPY directly liquefied by coal hydrogenation can be used as extraction oil, and the hydrogenated oil product produced in the hydrogenation upgrading reaction process HU of the high aromatic hydrocarbon produced oil RUPY directly liquefied by coal hydrogenation can also be used; however, the hydrogen donating solvent oil produced by the hydrogenation stabilization process of the high aromatic hydrocarbon-forming oil RUPY directly liquefied by coal hydrogenation is recommended as the extraction oil because:
① compared with the oil product upgraded by hydrogenation, the hydrogen-donating solvent oil is an extractant with moderate aromaticity, and according to the similar compatibility principle, the hydrogen-donating solvent with a certain aromaticity can more efficiently extract aromatic hydrocarbons with high aromaticity in the acidic water;
② the hydrogen donating miscella has a very low content of lower phenols and thus has a good ability to extract phenols;
③ the solubility of hydrogen-supplying solvent oil in water is lower than that of coal hydrogenated direct liquefaction oil (high aromatic hydrocarbon), thus the total oil content and proportion in acid water can be reduced;
④ the aromaticity of the hydrogen-supplying solvent oil is lower than that of the direct liquefied oil obtained by coal hydrogenation, so that the sulfur can be completely prevented from blackening during the process of preparing sulfur from acid gas;
⑤ the extracted oil WPY obtained in the acidic water extraction process can be used in the direct coal hydrogenation liquefaction process (can generate the phenol hydrogenation thermal cracking reaction and the hydrorefining deoxidation reaction), in the direct hydrogenation stabilization reaction process (can generate the phenol hydrorefining deoxidation reaction), in the direct coal hydrogenation liquefaction process, in the direct hydrogenation upgrading reaction process (can generate the phenol hydrorefining deoxidation reaction), and in a flexible process.
ZL201610550628.8 a process for the deoiling of a gas comprising normally gaseous hydrocarbons and normally liquid hydrocarbons of poor quality, comprising the steps of:
① obtaining gas PUG and oil APY containing normal gas hydrocarbon and inferior normal liquid hydrocarbon SD in the heat processing process PU of the low hydrogen content hydrocarbon HDS;
a thermal processing process PU of the low hydrogen content hydrocarbon HDS, which is selected from a heating distillation process, a coking process, a thermal cracking process, a shallow hydrogenation process, a heavy oil catalytic cracking process or a heavy oil catalytic cracking process;
the poor-quality conventional liquid hydrocarbon SD refers to hydrocarbons which cause environmental pollution by direct combustion and contains at least one part of organic sulfur or at least one part of organic nitrogen or at least one part of aromatic hydrocarbon;
at least a part of oil APY enters the hydro-upgrading process HU of the step ② to be used as hydrogenation raw oil HU-F1;
② in the hydro-upgrading process HU, under the condition of hydrogen and hydrogenation catalyst HUC, the hydro-base oil HU-F1 completes hydro-upgrading reaction HUR and converts into hydro-upgrading reaction product HUP;
separating the hydro-upgrading reaction product HUP to obtain a hydrocarbon-containing oil stream HUPY, and feeding the stream HUPY to the absorption process ASU in the step ③ to be used AS absorption oil AS;
③ in the absorption process ASU, gas PUG and absorption oil AS are contacted and separated for at least one time and converted into deoiled gas PUG-DO and rich absorption oil RS, and the rich absorption oil RS enters into the hydro-upgrading process HU to contact with the hydrogenation catalyst HUC for hydro-upgrading reaction.
When the present invention is used together with a method for deoiling ZL201610550628.8 gas containing conventional gas hydrocarbon and inferior conventional liquid hydrocarbon to form a series processing combined process, the following 2 modes are provided:
① absorbing oil AS, namely converting the absorbing oil AS into rich absorbing oil RS through a deoiling process of gas containing conventional gas hydrocarbon and inferior conventional liquid hydrocarbon, then converting the rich absorbing oil RS into extracted rich oil WPY AS extraction oil CY in an oil washing process WP of acidic water W01, and then extracting the rich oil WPY to a hydro-upgrading process WH, wherein the absorbing oil AS can be obtained based on the hydro-upgrading process WH for recycling;
② the extraction oil CY is converted into extraction rich oil WPY through the oil washing process WP of the acid water W01, the extraction rich oil WPY is used AS absorption oil AS, the extraction rich oil is converted into absorption rich oil RS through the deoiling process of the gas containing the conventional gas hydrocarbon and the inferior conventional liquid hydrocarbon, and then the absorption rich oil RS is subjected to the hydro-upgrading process WH, and the extraction oil CY can be obtained for recycling based on the hydro-upgrading process WH.
The method of the invention is not reported.
The invention aims to provide an oil washing method of acidic water obtained in the separation process of hydro-thermal cracking products of hydrocarbon materials.
Disclosure of Invention
The invention relates to an oil washing method of acidic water obtained in the separation process of hydro-thermal cracking products of hydrocarbon materials, which is characterized in that:
① in the process of hydrocracking reaction of hydrocarbon material RU, under the condition of mixed phase material containing hydrogen, liquid phase hydrocarbon and possible solid particles, the first raw material RUF1 at least containing carbon element and hydrogen element is converted into final hydrogenation reaction product RUP;
the final hydrogenation reaction product RUP, containing hydrogen sulfide, ammonia and possibly water, phenol components;
② separation process S100, separating hydrogen-rich gas, acidic water W00 containing hydrogen sulfide and possibly solid, and high-fraction oil mainly composed of conventional liquid hydrocarbon and possibly solid from the material containing hydrogen, hydrogen sulfide, ammonia and hydrocarbon components based on the final hydrogenation reaction product RUP;
in the separation process S100, there may be a hydrogenation product washing process RUP-W100 using washing water W99 for dissolving hydrogen sulfide, ammonia in a hydrogen, hydrogen sulfide, ammonia, hydrocarbon component-containing material based on the final hydrogenation reaction product RUP;
a stream based on the acid water W00 is used as the acid water W01 to be washed;
③ in the process of washing and extracting WP, the acid water W01 to be washed is contacted with the extracted oil CY at least once to be separated into washed acid water W05 and extracted rich oil WPY, and at least a part of the hydrocarbon oil with high aromaticity in the acid water W01 to be washed is transferred to the extracted rich oil WPY;
the washing effect is that the concentration of the high aromatic hydrocarbon in the acid water W05 after washing is lower than that of the high aromatic hydrocarbon in the acid water W01 to be washed and/or the concentration of the phenol in the acid water W05 after washing is lower than that of the phenol in the acid water W01 to be washed;
④ in the hydro-upgrading process HU, under the condition of hydrogen and hydrogenation catalyst HUC, the hydrocarbons based on the extracted rich oil WPY and other combined processing hydrocarbon materials complete the hydro-upgrading reaction HUR and are converted into a hydro-upgrading reaction product HUP;
separating the hydro-upgrading reaction product HUP to obtain a hydrocarbon-containing oil stream HUPY, possibly a portion of stream HUPY being passed to the washing extraction process WP described in step ③ for use as the extract oil CY.
In the invention, the 1 st common flow scheme is as follows:
② in separation process S100, there is a hydrogenation product washing process RUP-W100 using wash water W99;
⑤ in the sour WATER purification process SOURWATER-VS, removing hydrogen sulfide, ammonia and phenol components possibly existing in the washed sour WATER W05 to obtain purified WATER CLEAN-WATER;
at least a portion of the purified WATER CLEAN-WATER is passed to the hydroprocessed product wash RUP-W100 for use as wash WATER W99.
In the invention, the 2 nd common flow scheme is as follows:
② in separation process S100, there is a hydrogenation product washing process RUP-W100 using wash water W99;
⑤ in the sour WATER purification process SOURWATER-VS, removing hydrogen sulfide, ammonia and phenol component possibly existing in the washed sour WATER W05 to obtain purified WATER CLEAN-WATER, and obtaining semi-purified WATER HALF-CLEAN-WATER01 which is removed hydrogen sulfide and contains ammonia component and/or phenol component;
at least a portion of the semi-purified WATER HALF-CLEAN-WATER01 is passed to the hydroprocessed product washing process RUP-W100 for use as wash WATER W99.
In the invention, the 3 rd common flow scheme is as follows:
② in separation process S100, there is a hydrogenation product washing process RUP-W100 using wash water W99;
⑤ in the sour WATER purification process SOURWATER-VS, removing hydrogen sulfide, ammonia and phenol components possibly existing in the washed sour WATER W05 to obtain purified WATER CLEAN-WATER, and obtaining semi-purified WATER HALF-CLEAN-WATER02 which is removed hydrogen sulfide and ammonia and possibly contains phenol components;
at least a portion of the semi-purified WATER HALF-CLEAN-WATER02 is passed to the hydroprocessed product washing process RUP-W100 for use as wash WATER W99.
In the present invention, the RUF1, which is the first raw material containing at least carbon and hydrogen, is usually coal or heavy oil.
In the present invention, the first raw material RUF1 containing at least carbon and hydrogen is generally organic oxygen-containing coal or heavy oil.
In the invention, the hydrocracking reaction process RU of the hydrocarbon material can be selected from one or more of the following hydrogenation reaction processes:
① direct coal hydrogenation liquefaction reaction process, including direct coal hydrogenation liquefaction reaction process without hydrogen supply solvent oil, direct coal hydrogenation liquefaction reaction process with hydrogen supply solvent oil, coal hydrothermal liquefaction process, and kerosene co-refining process;
② hydrogenation of the liquefied oil obtained from the direct coal hydrogenation liquefaction reaction process;
③ hydrogenation process of oil product obtained from low temperature coal tar or distillate oil thereof or thermal processing process PU thereof, wherein the thermal processing process PU is selected from heating distillation process or coking process or thermal cracking process or shallow hydrogenation process or heavy oil catalytic cracking process;
④ hydrogenation process of oil product obtained from high temperature coal tar or distillate oil thereof or thermal processing process PU thereof, wherein the thermal processing process PU is selected from heating distillation process or coking process or thermal cracking process or shallow hydrogenation process or heavy oil catalytic cracking process;
⑤ hydrogenation process of heavy oil of shale oil or oil obtained from PU thermal processing process of shale oil, wherein the PU thermal processing process is selected from heating distillation process, coking process, thermal cracking process, shallow hydrogenation process, heavy oil catalytic cracking process or heavy oil catalytic cracking process;
⑥ hydrogenation process of oil product obtained by heavy oil thermal processing process PU of petroleum sand, wherein the thermal processing process PU is selected from heating distillation process, coking process, thermal cracking process, shallow hydrogenation process, heavy oil catalytic cracking process or heavy oil catalytic cracking process;
⑦ hydrogenation process of oil product obtained by the heavy oil thermal processing process PU, wherein the thermal processing process PU is selected from the heating distillation process, the coking process, the thermal cracking process, the shallow hydrogenation process, the heavy oil catalytic cracking process or the heavy oil catalytic cracking process;
⑧ other hydrocarbon oils with a weight content of aromatics higher than 45%, andor a weight content of gums higher than 15%, andor a weight content of asphaltenes higher than 5.0%.
In the invention, the first raw material RUF1 at least containing carbon element and hydrogen element is low-hydrogen-content hydrocarbon, and can be selected from one or more of the following materials:
① low temperature coal tar or distillate oil thereof or oil obtained by the thermal processing PU, wherein the thermal processing PU is selected from heating distillation process, coking process, thermal cracking process, shallow hydrogenation process, heavy oil catalytic cracking process or heavy oil catalytic cracking process;
② middle temperature coal tar or distillate oil thereof or oil obtained by the heat processing process PU, wherein the heat processing process PU is selected from heating distillation process or coking process or thermal cracking process or shallow hydrogenation process or heavy oil catalytic cracking process;
③ high temperature coal tar or distillate oil thereof or oil obtained by the thermal processing process PU, wherein the thermal processing process PU is selected from heating distillation process or coking process or thermal cracking process or shallow hydrogenation process or heavy oil catalytic cracking process;
④ coal liquefaction oil or distillate oil thereof obtained from coal liquefaction process or oil obtained from thermal processing process PU thereof, wherein the thermal processing process PU is selected from heating distillation process or coking process or thermal cracking process or shallow hydrogenation process or heavy oil catalytic cracking process;
⑤ shale oil or distillate oil thereof or oil obtained by the thermal processing process PU thereof, wherein the thermal processing process PU is selected from a heating distillation process, a coking process, a thermal cracking process, a shallow hydrogenation process, a heavy oil catalytic cracking process or a heavy oil catalytic cracking process;
⑥ petroleum sand-based heavy oil or oil obtained by the heat processing PU of the petroleum sand-based heavy oil, wherein the heat processing PU is selected from a heating distillation process, a coking process, a thermal cracking process, a shallow hydrogenation process, a heavy oil catalytic cracking process or a heavy oil catalytic cracking process;
⑦ thermal cracking of tar with petroleum-based wax oil;
⑧ oil obtained by the heavy oil thermal processing process PU, wherein the thermal processing process PU is selected from the heating distillation process, the coking process, the thermal cracking process, the light hydrogenation process, the heavy oil catalytic cracking process or the heavy oil catalytic cracking process;
⑨ the concentration of other polycyclic aromatic hydrocarbon is higher than 10%, and the total content of aromatic hydrocarbon is higher than 40%.
In the present invention, the operating conditions are generally:
③ in the process of washing and extracting WP, the acid water W01 to be washed is in contact separation with the extraction oil CY for 1-20 times;
④ the HU hydro-upgrading process is operated under the conditions of temperature 170-460 deg.C, pressure 4.0-28.0 MPa, and hydrogen/raw oil volume ratio 50-5000;
the extract oil CY obtained by separating the hydrogenation modified reaction product HUP mainly comprises hydrocarbon components with the conventional boiling point of 80-350 ℃.
In the present invention, the operation conditions of the extraction process WP are typically:
③ in the process of washing and extracting WP, the acid water W01 to be washed is in contact separation with the extraction oil CY for 1-20 times;
the extracted oil CY mainly comprises hydrocarbon components with the conventional boiling point of 80-350 ℃;
the operating conditions for the washing extraction process WP are: the pressure is 0.01-4.0 MPa, and the temperature is 10-75 ℃; defining the ratio of the weight flow of the extracted oil CY to the weight flow of the to-be-washed acidic water W01 as K900, wherein K900 is 0.01-0.5.
In the invention, the operation conditions of the WP in the washing extraction process are generally as follows:
③ in the process of washing and extracting WP, the acid water W01 to be washed is in contact separation with the extraction oil CY for 1-10 times;
the extracted oil CY mainly comprises hydrocarbon components with the conventional boiling point of 80-250 ℃;
the operating conditions for the washing extraction process WP are: the pressure is 0.1-1.0 MPa, and the temperature is 25-50 ℃; defining the ratio of the weight flow of the extracted oil CY to the weight flow of the to-be-washed acidic water W01 as K900, wherein the K900 is 0.05-0.20.
In the present invention, when applied to the suspension bed hydrocracking reaction process using the hydrogen donor solvent oil DS, the operation conditions of the washing extraction process WP may be generally as follows:
① hydrocracking reaction process RU of hydrocarbon material, which is a suspension bed hydrocracking reaction process of processing coal and/or heavy oil using hydrogen-supplying solvent oil DS;
the hydrogen donor solvent oil DS is from a solvent oil hydrogenation stabilization reaction process DS-MR matched with the hydrocarbon material hydrogenation thermal cracking reaction process RU;
③ in the process of washing and extracting WP, the acid water W01 to be washed is contacted with the extracted oil CY at least once to be separated into washed acid water W05 and extracted rich oil WPY, and at least a part of the hydrocarbon oil with high aromaticity in the acid water W01 to be washed is transferred to the extracted rich oil WPY;
the extracted oil CY is hydrocarbons obtained in the separation and fractionation process of the DS-MRP product in the hydrogenation and stabilization reaction process of the solvent oil.
In the present invention, when applied to the suspension bed hydrocracking reaction process using the hydrogen donor solvent oil DS, the operation conditions of the washing extraction process WP may be generally as follows:
① hydrocracking reaction process RU of hydrocarbon material, which is a hydrocracking reaction process of suspension bed of hydrogen-supplying solvent oil DS for processing coal and/or heavy oil;
the generated oil in the hydrogen material hydrogenation thermal cracking reaction process RU is subjected to RUP-FRAC fractionation to separate distillate RUP-FRAC-NY which mainly comprises hydrocarbon components with the conventional boiling point of 150-530 ℃; distilling distillate RUP-FRAC-NY to enter into a hydrogenation upgrading reaction process RDP;
③ in the process of washing and extracting WP, the acid water W01 to be washed is contacted with the extracted oil CY at least once to be separated into washed acid water W05 and extracted rich oil WPY, and at least a part of the hydrocarbon oil with high aromaticity in the acid water W01 to be washed is transferred to the extracted rich oil WPY;
the extracted oil CY is hydrocarbons obtained in the separation and fractionation process of a product RDP-P of the RDP in the hydrogenation upgrading reaction process.
When the invention is used together with a method for deoiling ZL201610550628.8 gas containing conventional gas hydrocarbon and inferior conventional liquid hydrocarbon to form a series processing combined process, the 1 st mode is as follows:
the extracted oil CY is rich absorption oil RS from the following de-oiling process X100 of a gas containing normal gaseous hydrocarbons and inferior normal liquid hydrocarbons;
the process X100 for the deoiling of a gas comprising normal gaseous hydrocarbons and inferior normal liquid hydrocarbons comprises the following steps:
① obtaining gas PUG and oil APY containing normal gas hydrocarbon and inferior normal liquid hydrocarbon SD in the heat processing process PU of the low hydrogen content hydrocarbon HDS;
a thermal processing process PU of the low hydrogen content hydrocarbon HDS, which is selected from a heating distillation process, a coking process, a thermal cracking process, a shallow hydrogenation process, a heavy oil catalytic cracking process or a heavy oil catalytic cracking process;
the poor-quality conventional liquid hydrocarbon SD refers to hydrocarbons which cause environmental pollution by direct combustion and contains at least one part of organic sulfur or at least one part of organic nitrogen or at least one part of aromatic hydrocarbon;
at least a part of oil APY enters the hydro-upgrading process HU of the step ② to be used as hydrogenation raw oil HU-F1;
② in the hydro-upgrading process HU, under the condition of hydrogen and hydrogenation catalyst HUC, the hydro-base oil HU-F1 completes hydro-upgrading reaction HUR and converts into hydro-upgrading reaction product HUP;
separating the hydro-upgrading reaction product HUP to obtain a hydrocarbon-containing oil stream HUPY, and feeding the stream HUPY to the absorption process ASU in the step ③ to be used AS absorption oil AS;
③ in the absorption process ASU, gas PUG and absorption oil AS are contacted and separated for at least one time and converted into deoiled gas PUG-D0 and rich absorption oil RS, and the rich absorption oil RS enters into the hydro-upgrading process HU and contacts with the hydrogenation catalyst HUC to carry out hydro-upgrading reaction.
When the present invention is used together with a method for deoiling ZL201610550628.8 gas containing conventional gas hydrocarbon and inferior conventional liquid hydrocarbon to form a series processing combined process, the 2 nd mode is as follows:
in the process of washing and extracting WP, the acid water W01 to be washed is contacted and separated with the extraction oil CY at least once to form washed acid water W05 and extracted rich oil WPY, and at least part of high-aromaticity hydrocarbon oil in the acid water W01 to be washed is transferred to the extracted rich oil WPY;
an extract rich oil WPY for use AS absorption oil AS in the following de-oiling process X100 of a gas containing normal gaseous hydrocarbons and inferior normal liquid hydrocarbons;
the process X100 for the deoiling of a gas comprising normal gaseous hydrocarbons and inferior normal liquid hydrocarbons comprises the following steps:
① obtaining gas PUG and oil APY containing normal gas hydrocarbon and inferior normal liquid hydrocarbon SD in the heat processing process PU of the low hydrogen content hydrocarbon HDS;
a thermal processing process PU of the low hydrogen content hydrocarbon HDS, which is selected from a heating distillation process, a coking process, a thermal cracking process, a shallow hydrogenation process, a heavy oil catalytic cracking process or a heavy oil catalytic cracking process;
the poor-quality conventional liquid hydrocarbon SD refers to hydrocarbons which cause environmental pollution by direct combustion and contains at least one part of organic sulfur or at least one part of organic nitrogen or at least one part of aromatic hydrocarbon;
at least a part of oil APY enters the hydro-upgrading process HU of the step ② to be used as hydrogenation raw oil HU-F1;
② in the hydro-upgrading process HU, under the condition of hydrogen and hydrogenation catalyst HUC, the hydro-base oil HU-F1 completes hydro-upgrading reaction HUR and converts into hydro-upgrading reaction product HUP;
separating the hydro-upgrading reaction product HUP to obtain a hydrocarbon-containing oil stream HUPY, and feeding the stream HUPY to the absorption process ASU in the step ③ to be used AS absorption oil AS;
③ in the absorption process ASU, gas PUG and absorption oil AS are contacted and separated for at least one time and converted into deoiled gas PUG-D0 and rich absorption oil RS, and the rich absorption oil RS enters into the hydro-upgrading process HU and contacts with the hydrogenation catalyst HUC to carry out hydro-upgrading reaction.
Detailed Description
The present invention is described in detail below.
The pressure in the present invention refers to absolute pressure.
The conventional boiling point of the invention refers to the vapor-liquid equilibrium temperature of a substance at one atmospheric pressure.
The conventional boiling range as referred to herein refers to the conventional boiling range of the distillate fraction.
The specific gravity of the present invention refers to the ratio of the density of a liquid at ordinary pressure and 15.6 ℃ to the density of a liquid at ordinary pressure and 15.6 ℃ unless otherwise specified.
The compositions or concentrations or amounts or yield values of the components described herein are weight basis values unless otherwise specified.
The conventional gaseous hydrocarbon refers to hydrocarbon which is gaseous under conventional conditions, and comprises methane, ethane, propane and butane.
The conventional liquid hydrocarbon refers to hydrocarbon which is liquid under conventional conditions, and includes pentane and hydrocarbon with higher boiling point.
The impurity elements in the invention refer to non-hydrogen, non-carbon and non-metal components in the raw oil, such as oxygen, sulfur, nitrogen, chlorine and the like.
The impurity component in the invention refers to the hydrogenation conversion product of non-hydrocarbon component in the raw oil, such as water, ammonia, hydrogen sulfide, hydrogen chloride and the like.
The light hydrocarbon, which is a naphtha component, referred to herein is a conventional liquid hydrocarbon having a conventional boiling point of less than 200 ℃.
The diesel component refers to hydrocarbons with a conventional boiling point of 200-350 ℃.
The wax oil component refers to hydrocarbons with the conventional boiling point of 350-530 ℃.
The medium hydrocarbon refers to hydrocarbon with a conventional boiling point of 230-400 ℃.
The heavy hydrocarbon refers to hydrocarbon with a conventional boiling point higher than 350 ℃.
The hydrogen-oil volume ratio refers to the ratio of the standard state volume flow of hydrogen to the volume flow of a specified oil material flow at normal pressure and 20 ℃.
The aromatic ring number of the polycyclic aromatic hydrocarbon is more than or equal to 3.
The hydrogen donor refers to hydrocarbon components with hydrogen donor function in the coal hydrogenation direct liquefaction reaction process, the heavy oil hydrogenation reaction process and the kerosene co-refining hydrogenation reaction process, and the hydrogen donor comprises partially saturated bicyclic aromatic hydrocarbon and partially saturated polycyclic aromatic hydrocarbon. In the hydrogen supply hydrocarbon, the hydrogen supply speed of a dihydro body is higher than that of a tetrahydro body, and the hydrogen supply speed of the dihydro body of tricyclic aromatic hydrocarbon is higher or lower than that of the dihydro body of bicyclic aromatic hydrocarbon; tests have demonstrated that polycyclic aromatic hydrocarbons, although not having a hydrogen donating ability, have the ability to transfer hydrogen. The relative hydrogen supply rates at 400 ℃ for the following components were as follows:
the coal hydrogenation direct liquefaction process is described below.
The direct coal hydrogenation liquefaction process is a method for directly liquefying coal by hydrogenation in the presence of solvent oil, and can be divided into the following processes according to the difference of the solvent oil and a catalyst, the difference of a pyrolysis mode and a hydrogenation mode and the difference of process conditions:
① pyrolysis liquefaction method, wherein the coal is pyrolyzed and extracted by heavy solvent to obtain low ash extract (called as bentonite), and the heavy oil is extracted by light solvent under supercritical condition to obtain heavy oil as main oil, the method does not use hydrogen, the yield of the former process is high, but the product is solid, and the extraction rate of the latter process such as supercritical extraction (SCE) is not too high;
② solvent hydrogenation extraction liquefaction method, such as solvent refining coal method 1 and II (SRC-1 and SRC-II), hydrogen supply solvent method EDS, Japan New energy development organization liquefaction method (NEDOL), etc., using hydrogen, but the pressure is not too high, the solvent naphtha has obvious effect;
③ high pressure catalytic hydrogenation, such as the German old and New liquefaction process (IG and NewLG) and the United states hydrogen Coal process (H-Coal) belong to this category;
④ Combined processing method of coal and residual oil (C0. processing), which comprises passing residual oil as solvent oil through a reactor together with coal in one step without circulating oil, and performing hydrocracking on the residual oil to obtain light oil;
⑤ Dry distillation liquefaction method comprises pyrolyzing coal to obtain tar, hydrocracking tar, and upgrading;
⑥ underground liquefaction is carried out by injecting solvent into underground coal bed to depolymerize and dissolve coal, adding fluid impact force to break down coal, suspending incompletely dissolved coal in solvent, pumping out solution, and separating.
In the direct coal liquefaction method, most of the direct coal hydrogenation liquefaction oil preparation processes belong to the direct coal hydrogenation liquefaction process, no matter what kind of direct coal hydrogenation liquefaction process, the aim is to obtain an oil product, the sought function is coal-to-oil, the necessary chemical change is coal hydrogenation, the common characteristics of the prior art are that solvent oil and a catalyst are used, the conventional boiling range of the solvent oil is generally 200-450 ℃, most of the solvent oil is 200-400 ℃, most of the solvent oil is distilled oil, and most of the contained aromatic hydrocarbon is aromatic hydrocarbon with 2-4 ring structures. Therefore, no matter what kind of coal hydrogenation direct liquefaction process, the produced external oil discharge, coal hydrogenation direct liquefaction oil (usually coal hydrogenation direct liquefaction light oil) or coal hydrogenation direct liquefaction oil modified oil can be processed by the method of the present invention as long as the composition has the characteristics of the raw material composition of the present invention.
The patent CN100547055C discloses a hot-melt catalysis method for preparing liquid fuel from lignite, which belongs to the direct liquefaction process of lignite through medium-pressure hydrogenation, and comprises two processes of a coal hydrogenation direct liquefaction reaction process and a coal hydrogenation direct liquefaction oil hydrogenation modification process. In order to improve the conversion rate of direct coal liquefaction and realize that coal raw materials enter a direct coal hydrogenation liquefaction reactor, coal is usually made into coal powder before entering the direct coal hydrogenation liquefaction reactor, the coal powder is prepared into oil coal slurry with solvent oil with good hydrogen supply capacity, and the oil coal slurry enters the direct coal hydrogenation liquefaction reactor after being pressurized and heated.
The coal hydrogenation direct liquefaction reaction process refers to a reaction process of directly carrying out carbon-carbon bond thermal cracking and hydrogenation liquefaction on coal under certain operation conditions (such as operation temperature, operation pressure, solvent oil/coal weight ratio, hydrogen/solvent oil volume ratio and a proper hydrogenation catalyst) by taking coal and possibly existing molecular hydrogen as raw materials and taking a specific oil product (usually, hydrogenation modified oil of the coal hydrogenation direct liquefaction oil) as hydrogen supply solvent oil.
The coal hydrogenation direct liquefaction oil refers to an oil product produced in the coal hydrogenation direct liquefaction reaction process, exists in the effluent of the coal hydrogenation liquefaction reaction, and is a comprehensive reaction product based on hydrogen supply solvent oil, reaction consumed coal and reaction transferred hydrogen.
After the coal hydrogenation direct liquefaction reaction process is normally operated, the hydrogen-supplying solvent oil is generally hydrogenated modified oil of coal hydrogenation direct liquefaction oil (usually distillate oil with a conventional boiling range higher than 165 ℃) produced in the coal hydrogenation direct liquefaction reaction process, and the main objective of the coal hydrogenation direct liquefaction oil hydrogenation modification process is to produce the solvent oil for the coal hydrogenation direct liquefaction reaction process, specifically to improve the content of components with good hydrogen supply function in oil products, such as naphthenic benzenes and dicycloalkylbenzenes, and based on the fact that the coal hydrogenation direct liquefaction oil contains a large amount of bicyclic aromatic hydrocarbons and a large amount of tricyclic aromatic hydrocarbons, the coal hydrogenation direct liquefaction oil hydrogenation modification process is a hydrogenation process with moderate aromatic hydrocarbon saturation.
The final objective of the coal hydrogenation direct liquefaction reaction process is to produce an oil product supplied externally, and usually, the hydrogenated modified oil produced in the coal hydrogenation direct liquefaction oil hydrogenation modification process is divided into two parts: one part is used as hydrogen supply solvent oil for the coal hydrogenation direct liquefaction reaction process, and the other part is used as external oil discharge in the coal hydrogenation direct liquefaction oil preparation process. Usually, at least a part of the coal hydrogenation direct liquefaction light oil generated in the coal hydrogenation direct liquefaction reaction process is used as external oil discharge A in the coal-to-oil process, the rest of the coal hydrogenation direct liquefaction oil is used as raw oil in the coal hydrogenation direct liquefaction process to produce hydrogen supply solvent oil and external oil B for the coal hydrogenation direct liquefaction reaction process, at this time, two paths of external oil discharge A and B exist, and the final destination of the two paths of external oil discharge A and B is usually to produce high-quality oil products such as diesel oil fraction and naphtha fraction through a deep hydrogenation upgrading process.
The hydrogen donor solvent oil component is a hydrocarbon of which the aromaticity is lower than that of the direct coal hydrogenation liquefied oil hydrocarbon component with the same number of carbon atoms, so compared with the direct coal hydrogenation liquefied oil hydrocarbon component, the hydrogen donor solvent oil component has the following characteristics:
① has low aromaticity and therefore low solubility in water;
② retains a certain aromaticity, has high solubility for directly liquefying hydrocarbon components of coal hydrogenation, and is favorable for being used as extraction oil CY;
③ has low aromatic degree, small acting force with water molecules, and easy sedimentation separation;
④ has low aromaticity and is easy to burn completely.
The invention relates to an oil washing method of acidic water obtained in the separation process of hydro-thermal cracking products of hydrocarbon materials, which is characterized in that:
① in the process of hydrocracking reaction of hydrocarbon material RU, under the condition of mixed phase material containing hydrogen, liquid phase hydrocarbon and possible solid particles, the first raw material RUF1 at least containing carbon element and hydrogen element is converted into final hydrogenation reaction product RUP;
the final hydrogenation reaction product RUP, containing hydrogen sulfide, ammonia and possibly water, phenol components;
② separation process S100, separating hydrogen-rich gas, acidic water W00 containing hydrogen sulfide and possibly solid, and high-fraction oil mainly composed of conventional liquid hydrocarbon and possibly solid from the material containing hydrogen, hydrogen sulfide, ammonia and hydrocarbon components based on the final hydrogenation reaction product RUP;
in the separation process S100, there may be a hydrogenation product washing process RUP-W100 using washing water W99 for dissolving hydrogen sulfide, ammonia in a hydrogen, hydrogen sulfide, ammonia, hydrocarbon component-containing material based on the final hydrogenation reaction product RUP;
a stream based on the acid water W00 is used as the acid water W01 to be washed;
③ in the process of washing and extracting WP, the acid water W01 to be washed is contacted with the extracted oil CY at least once to be separated into washed acid water W05 and extracted rich oil WPY, and at least a part of the hydrocarbon oil with high aromaticity in the acid water W01 to be washed is transferred to the extracted rich oil WPY;
the washing effect is that the concentration of the high aromatic hydrocarbon in the acid water W05 after washing is lower than that of the high aromatic hydrocarbon in the acid water W01 to be washed and/or the concentration of the phenol in the acid water W05 after washing is lower than that of the phenol in the acid water W01 to be washed;
④ in the hydro-upgrading process HU, under the condition of hydrogen and hydrogenation catalyst HUC, the hydrocarbons based on the extracted rich oil WPY and other combined processing hydrocarbon materials complete the hydro-upgrading reaction HUR and are converted into a hydro-upgrading reaction product HUP;
separating the hydro-upgrading reaction product HUP to obtain a hydrocarbon-containing oil stream HUPY, possibly a portion of stream HUPY being passed to the washing extraction process WP described in step ③ for use as the extract oil CY.
In the invention, the 1 st common flow scheme is as follows:
② in separation process S100, there is a hydrogenation product washing process RUP-W100 using wash water W99;
⑤ in the sour WATER purification process SOURWATER-VS, removing hydrogen sulfide, ammonia and phenol components possibly existing in the washed sour WATER W05 to obtain purified WATER CLEAN-WATER;
at least a portion of the purified WATER CLEAN-WATER is passed to the hydroprocessed product wash RUP-W100 for use as wash WATER W99.
In the invention, the 2 nd common flow scheme is as follows:
② in separation process S100, there is a hydrogenation product washing process RUP-W100 using wash water W99;
⑤ in the sour WATER purification process SOURWATER-VS, removing hydrogen sulfide, ammonia and phenol component possibly existing in the washed sour WATER W05 to obtain purified WATER CLEAN-WATER, and obtaining semi-purified WATER HALF-CLEAN-WATER01 which is removed hydrogen sulfide and contains ammonia component and/or phenol component;
at least a portion of the semi-purified WATER HALF-CLEAN-WATER01 is passed to the hydroprocessed product washing process RUP-W100 for use as wash WATER W99.
In the invention, the 3 rd common flow scheme is as follows:
② in separation process S100, there is a hydrogenation product washing process RUP-W100 using wash water W99;
⑤ in the sour WATER purification process SOURWATER-VS, removing hydrogen sulfide, ammonia and phenol components possibly existing in the washed sour WATER W05 to obtain purified WATER CLEAN-WATER, and obtaining semi-purified WATER HALF-CLEAN-WATER02 which is removed hydrogen sulfide and ammonia and possibly contains phenol components;
at least a portion of the semi-purified WATER HALF-CLEAN-WATER02 is passed to the hydroprocessed product washing process RUP-W100 for use as wash WATER W99.
In the present invention, the RUF1, which is the first raw material containing at least carbon and hydrogen, is usually coal or heavy oil.
In the present invention, the first raw material RUF1 containing at least carbon and hydrogen is generally organic oxygen-containing coal or heavy oil.
In the invention, the hydrocracking reaction process RU of the hydrocarbon material can be selected from one or more of the following hydrogenation reaction processes:
① direct coal hydrogenation liquefaction reaction process, including direct coal hydrogenation liquefaction reaction process without hydrogen supply solvent oil, direct coal hydrogenation liquefaction reaction process with hydrogen supply solvent oil, coal hydrothermal liquefaction process, and kerosene co-refining process;
② hydrogenation of the liquefied oil obtained from the direct coal hydrogenation liquefaction reaction process;
③ hydrogenation process of oil product obtained from low temperature coal tar or distillate oil thereof or thermal processing process PU thereof, wherein the thermal processing process PU is selected from heating distillation process or coking process or thermal cracking process or shallow hydrogenation process or heavy oil catalytic cracking process;
④ hydrogenation process of oil product obtained from high temperature coal tar or distillate oil thereof or thermal processing process PU thereof, wherein the thermal processing process PU is selected from heating distillation process or coking process or thermal cracking process or shallow hydrogenation process or heavy oil catalytic cracking process;
⑤ hydrogenation process of heavy oil of shale oil or oil obtained from PU thermal processing process of shale oil, wherein the PU thermal processing process is selected from heating distillation process, coking process, thermal cracking process, shallow hydrogenation process, heavy oil catalytic cracking process or heavy oil catalytic cracking process;
⑥ hydrogenation process of oil product obtained by heavy oil thermal processing process PU of petroleum sand, wherein the thermal processing process PU is selected from heating distillation process, coking process, thermal cracking process, shallow hydrogenation process, heavy oil catalytic cracking process or heavy oil catalytic cracking process;
⑦ hydrogenation process of oil product obtained by the heavy oil thermal processing process PU, wherein the thermal processing process PU is selected from the heating distillation process, the coking process, the thermal cracking process, the shallow hydrogenation process, the heavy oil catalytic cracking process or the heavy oil catalytic cracking process;
⑧ other hydrocarbon oils with a weight content of aromatics higher than 45%, andor a weight content of gums higher than 15%, andor a weight content of asphaltenes higher than 5.0%.
In the invention, the first raw material RUF1 at least containing carbon element and hydrogen element is low-hydrogen-content hydrocarbon, and can be selected from one or more of the following materials:
① low temperature coal tar or distillate oil thereof or oil obtained by the thermal processing PU, wherein the thermal processing PU is selected from heating distillation process, coking process, thermal cracking process, shallow hydrogenation process, heavy oil catalytic cracking process or heavy oil catalytic cracking process;
② middle temperature coal tar or distillate oil thereof or oil obtained by the heat processing process PU, wherein the heat processing process PU is selected from heating distillation process or coking process or thermal cracking process or shallow hydrogenation process or heavy oil catalytic cracking process;
③ high temperature coal tar or distillate oil thereof or oil obtained by the thermal processing process PU, wherein the thermal processing process PU is selected from heating distillation process or coking process or thermal cracking process or shallow hydrogenation process or heavy oil catalytic cracking process;
④ coal liquefaction oil or distillate oil thereof obtained from coal liquefaction process or oil obtained from thermal processing process PU thereof, wherein the thermal processing process PU is selected from heating distillation process or coking process or thermal cracking process or shallow hydrogenation process or heavy oil catalytic cracking process;
⑤ shale oil or distillate oil thereof or oil obtained by the thermal processing process PU thereof, wherein the thermal processing process PU is selected from a heating distillation process, a coking process, a thermal cracking process, a shallow hydrogenation process, a heavy oil catalytic cracking process or a heavy oil catalytic cracking process;
⑥ petroleum sand-based heavy oil or oil obtained by the heat processing PU of the petroleum sand-based heavy oil, wherein the heat processing PU is selected from a heating distillation process, a coking process, a thermal cracking process, a shallow hydrogenation process, a heavy oil catalytic cracking process or a heavy oil catalytic cracking process;
⑦ thermal cracking of tar with petroleum-based wax oil;
⑧ oil obtained by the heavy oil thermal processing process PU, wherein the thermal processing process PU is selected from the heating distillation process, the coking process, the thermal cracking process, the light hydrogenation process, the heavy oil catalytic cracking process or the heavy oil catalytic cracking process;
⑨ the concentration of other polycyclic aromatic hydrocarbon is higher than 10%, and the total content of aromatic hydrocarbon is higher than 40%.
In the present invention, the operating conditions are generally:
③ in the process of washing and extracting WP, the acid water W01 to be washed is in contact separation with the extraction oil CY for 1-20 times;
④ the HU hydro-upgrading process is operated under the conditions of temperature 170-460 deg.C, pressure 4.0-28.0 MPa, and hydrogen/raw oil volume ratio 50-5000;
the extract oil CY obtained by separating the hydrogenation modified reaction product HUP mainly comprises hydrocarbon components with the conventional boiling point of 80-350 ℃.
In the present invention, the operation conditions of the extraction process WP are typically:
③ in the process of washing and extracting WP, the acid water W01 to be washed is in contact separation with the extraction oil CY for 1-20 times;
the extracted oil CY mainly comprises hydrocarbon components with the conventional boiling point of 80-350 ℃;
the operating conditions for the washing extraction process WP are: the pressure is 0.01-4.0 MPa, and the temperature is 10-75 ℃; defining the ratio of the weight flow of the extracted oil CY to the weight flow of the to-be-washed acidic water W01 as K900, wherein K900 is 0.01-0.5.
In the invention, the operation conditions of the WP in the washing extraction process are generally as follows:
③ in the process of washing and extracting WP, the acid water W01 to be washed is in contact separation with the extraction oil CY for 1-10 times;
the extracted oil CY mainly comprises hydrocarbon components with the conventional boiling point of 80-250 ℃;
the operating conditions for the washing extraction process WP are: the pressure is 0.1-1.0 MPa, and the temperature is 25-50 ℃; defining the ratio of the weight flow of the extracted oil CY to the weight flow of the to-be-washed acidic water W01 as K900, wherein the K900 is 0.05-0.20.
In the present invention, when applied to the suspension bed hydrocracking reaction process using the hydrogen donor solvent oil DS, the operation conditions of the washing extraction process WP may be generally as follows:
① hydrocracking reaction process RU of hydrocarbon material, which is a suspension bed hydrocracking reaction process of processing coal and/or heavy oil using hydrogen-supplying solvent oil DS;
the hydrogen donor solvent oil DS is from a solvent oil hydrogenation stabilization reaction process DS-MR matched with the hydrocarbon material hydrogenation thermal cracking reaction process RU;
③ in the process of washing and extracting WP, the acid water W01 to be washed is contacted with the extracted oil CY at least once to be separated into washed acid water W05 and extracted rich oil WPY, and at least a part of the hydrocarbon oil with high aromaticity in the acid water W01 to be washed is transferred to the extracted rich oil WPY;
the extracted oil CY is hydrocarbons obtained in the separation and fractionation process of the DS-MRP product in the hydrogenation and stabilization reaction process of the solvent oil.
In the present invention, when applied to the suspension bed hydrocracking reaction process using the hydrogen donor solvent oil DS, the operation conditions of the washing extraction process WP may be generally as follows:
① hydrocracking reaction process RU of hydrocarbon material, which is a hydrocracking reaction process of suspension bed of hydrogen-supplying solvent oil DS for processing coal and/or heavy oil;
the generated oil in the hydrogen material hydrogenation thermal cracking reaction process RU is subjected to RUP-FRAC fractionation to separate distillate RUP-FRAC-NY which mainly comprises hydrocarbon components with the conventional boiling point of 150-530 ℃; distilling distillate RUP-FRAC-NY to enter into a hydrogenation upgrading reaction process RDP;
③ in the process of washing and extracting WP, the acid water W01 to be washed is contacted with the extracted oil CY at least once to be separated into washed acid water W05 and extracted rich oil WPY, and at least a part of the hydrocarbon oil with high aromaticity in the acid water W01 to be washed is transferred to the extracted rich oil WPY;
the extracted oil CY is hydrocarbons obtained in the separation and fractionation process of a product RDP-P of the RDP in the hydrogenation upgrading reaction process.
When the invention is used together with a method for deoiling ZL201610550628.8 gas containing conventional gas hydrocarbon and inferior conventional liquid hydrocarbon to form a series processing combined process, the 1 st mode is as follows:
the extracted oil CY is rich absorption oil RS from the following de-oiling process X100 of a gas containing normal gaseous hydrocarbons and inferior normal liquid hydrocarbons;
the process X100 for the deoiling of a gas comprising normal gaseous hydrocarbons and inferior normal liquid hydrocarbons comprises the following steps:
① obtaining gas PUG and oil APY containing normal gas hydrocarbon and inferior normal liquid hydrocarbon SD in the heat processing process PU of the low hydrogen content hydrocarbon HDS;
a thermal processing process PU of the low hydrogen content hydrocarbon HDS, which is selected from a heating distillation process, a coking process, a thermal cracking process, a shallow hydrogenation process, a heavy oil catalytic cracking process or a heavy oil catalytic cracking process;
the poor-quality conventional liquid hydrocarbon SD refers to hydrocarbons which cause environmental pollution by direct combustion and contains at least one part of organic sulfur or at least one part of organic nitrogen or at least one part of aromatic hydrocarbon;
at least a part of oil APY enters the hydro-upgrading process HU of the step ② to be used as hydrogenation raw oil HU-F1;
② in the hydro-upgrading process HU, under the condition of hydrogen and hydrogenation catalyst HUC, the hydro-base oil HU-F1 completes hydro-upgrading reaction HUR and converts into hydro-upgrading reaction product HUP;
separating the hydro-upgrading reaction product HUP to obtain a hydrocarbon-containing oil stream HUPY, and feeding the stream HUPY to the absorption process ASU in the step ③ to be used AS absorption oil AS;
③ in the absorption process ASU, gas PUG and absorption oil AS are contacted and separated for at least one time and converted into deoiled gas PUG-DO and rich absorption oil RS, and the rich absorption oil RS enters into the hydro-upgrading process HU to contact with the hydrogenation catalyst HUC for hydro-upgrading reaction.
When the present invention is used together with a method for deoiling ZL201610550628.8 gas containing conventional gas hydrocarbon and inferior conventional liquid hydrocarbon to form a series processing combined process, the 2 nd mode is as follows:
in the process of washing and extracting WP, the acid water W01 to be washed is contacted and separated with the extraction oil CY at least once to form washed acid water W05 and extracted rich oil WPY, and at least part of high-aromaticity hydrocarbon oil in the acid water W01 to be washed is transferred to the extracted rich oil WPY;
an extract rich oil WPY for use AS absorption oil AS in the following de-oiling process X100 of a gas containing normal gaseous hydrocarbons and inferior normal liquid hydrocarbons;
the process X100 for the deoiling of a gas comprising normal gaseous hydrocarbons and inferior normal liquid hydrocarbons comprises the following steps:
① obtaining gas PUG and oil APY containing normal gas hydrocarbon and inferior normal liquid hydrocarbon SD in the heat processing process PU of the low hydrogen content hydrocarbon HDS;
a thermal processing process PU of the low hydrogen content hydrocarbon HDS, which is selected from a heating distillation process, a coking process, a thermal cracking process, a shallow hydrogenation process, a heavy oil catalytic cracking process or a heavy oil catalytic cracking process;
the poor-quality conventional liquid hydrocarbon SD refers to hydrocarbons which cause environmental pollution by direct combustion and contains at least one part of organic sulfur or at least one part of organic nitrogen or at least one part of aromatic hydrocarbon;
at least a part of oil APY enters the hydro-upgrading process HU of the step ② to be used as hydrogenation raw oil HU-F1;
② in the hydro-upgrading process HU, under the condition of hydrogen and hydrogenation catalyst HUC, the hydro-base oil HU-F1 completes hydro-upgrading reaction HUR and converts into hydro-upgrading reaction product HUP;
separating the hydro-upgrading reaction product HUP to obtain a hydrocarbon-containing oil stream HUPY, and feeding the stream HUPY to the absorption process ASU in the step ③ to be used AS absorption oil AS;
③ in the absorption process ASU, gas PUG and absorption oil AS are contacted and separated for at least one time and converted into deoiled gas PUG-DO and rich absorption oil RS, and the rich absorption oil RS enters into the hydro-upgrading process HU to contact with the hydrogenation catalyst HUC for hydro-upgrading reaction.
The invention has the advantages that:
①, the concentration of high aromatic hydrocarbon in the acidic water to be purified can be reduced, and the phenomenon that sulfur is blackened due to incomplete combustion of the high aromatic hydrocarbon in the process of preparing sulfur from acidic gas by using hydrogen sulfide gas from the acidic water is avoided;
② after the concentration of high aromatic hydrocarbon of the acidic water to be purified is reduced, the process of filtering and removing solid of the acidic water to be purified is facilitated, and the solid removal rate can be improved, so that the flow channel blocking speed of a heat exchanger and a stripper tower tray in the process of purifying the acidic water is reduced, the equipment is maintained in a high-efficiency process state for a long time, the unplanned shutdown maintenance frequency is reduced, and the device operation rate is improved;
③ can be used in combination with a gas deoiling method of ZL201610550628.8 containing conventional gas hydrocarbon and inferior conventional liquid hydrocarbon to form a series processing combination process to improve the utilization rate of absorption oil or extraction oil.
Claims (15)
1. The oil washing method of the acidic water obtained in the separation process of the hydro-thermal cracking products of the hydrocarbon material is characterized in that:
① in the process of hydrocracking reaction of hydrocarbon material RU, under the condition of mixed phase material containing hydrogen, liquid phase hydrocarbon and possible solid particles, the first raw material RUF1 at least containing carbon element and hydrogen element is converted into final hydrogenation reaction product RUP;
the final hydrogenation reaction product RUP, containing hydrogen sulfide, ammonia and possibly water, phenol components;
② separation process S100, separating hydrogen-rich gas, acidic water W00 containing hydrogen sulfide and possibly solid, and high-fraction oil mainly composed of conventional liquid hydrocarbon and possibly solid from the material containing hydrogen, hydrogen sulfide, ammonia and hydrocarbon components based on the final hydrogenation reaction product RUP;
in the separation process S100, there may be a hydrogenation product washing process RUP-W100 using washing water W99 for dissolving hydrogen sulfide, ammonia in a hydrogen, hydrogen sulfide, ammonia, hydrocarbon component-containing material based on the final hydrogenation reaction product RUP;
a stream based on the acid water W00 is used as the acid water W01 to be washed;
③ in the process of washing and extracting WP, the acid water W01 to be washed is contacted with the extracted oil CY at least once to be separated into washed acid water W05 and extracted rich oil WPY, and at least a part of the hydrocarbon oil with high aromaticity in the acid water W01 to be washed is transferred to the extracted rich oil WPY;
the washing effect is that the concentration of the high aromatic hydrocarbon in the acid water W05 after washing is lower than that of the high aromatic hydrocarbon in the acid water W01 to be washed and/or the concentration of the phenol in the acid water W05 after washing is lower than that of the phenol in the acid water W01 to be washed;
④ in the hydro-upgrading process HU, under the condition of hydrogen and hydrogenation catalyst HUC, the hydrocarbons based on the extracted rich oil WPY and other combined processing hydrocarbon materials complete the hydro-upgrading reaction HUR and are converted into a hydro-upgrading reaction product HUP;
separating the hydro-upgrading reaction product HUP to obtain a hydrocarbon-containing oil stream HUPY, possibly a portion of stream HUPY being passed to the washing extraction process WP described in step ③ for use as the extract oil CY.
2. The method of claim 1, further comprising:
② in separation process S100, there is a hydrogenation product washing process RUP-W100 using wash water W99;
⑤ in the sour WATER purification process SOURWATER-VS, removing hydrogen sulfide, ammonia and phenol components possibly existing in the washed sour WATER W05 to obtain purified WATER CLEAN-WATER;
at least a portion of the purified WATER CLEAN-WATER is passed to the hydroprocessed product wash RUP-W100 for use as wash WATER W99.
3. The method of claim 1, further comprising:
② in separation process S100, there is a hydrogenation product washing process RUP-W100 using wash water W99;
⑤ in the sour WATER purification process SOURWATER-VS, removing hydrogen sulfide, ammonia and phenol component possibly existing in the washed sour WATER W05 to obtain purified WATER CLEAN-WATER, and obtaining semi-purified WATER HALF-CLEAN-WATER01 which is removed hydrogen sulfide and contains ammonia component and/or phenol component;
at least a portion of the semi-purified WATER HALF-CLEAN-WATER01 is passed to the hydroprocessed product washing process RUP-W100 for use as wash WATER W99.
4. The method of claim 1, further comprising:
② in separation process S100, there is a hydrogenation product washing process RUP-W100 using wash water W99;
⑤ in the sour WATER purification process SOURWATER-VS, removing hydrogen sulfide, ammonia and phenol components possibly existing in the washed sour WATER W05 to obtain purified WATER CLEAN-WATER, and obtaining semi-purified WATER HALF-CLEAN-WATER02 which is removed hydrogen sulfide and ammonia and possibly contains phenol components;
at least a portion of the semi-purified WATER HALF-CLEAN-WATER02 is passed to the hydroprocessed product washing process RUP-W100 for use as wash WATER W99.
5. The method of claim 1 or 2 or 3 or 4, wherein:
the first raw material RUF1 at least containing carbon element and hydrogen element is coal or heavy oil.
6. The method of claim 1 or 2 or 3 or 4, wherein:
the first raw material RUF1 containing at least carbon and hydrogen is organic oxygen-containing coal or heavy oil.
7. The method of claim 1 or 2 or 3 or 4, wherein:
the hydrocarbon material hydrogenation thermal cracking reaction process RU is selected from one or more of the following hydrogenation reaction processes:
① direct coal hydrogenation liquefaction reaction process, including direct coal hydrogenation liquefaction reaction process without hydrogen supply solvent oil, direct coal hydrogenation liquefaction reaction process with hydrogen supply solvent oil, coal hydrothermal liquefaction process, and kerosene co-refining process;
② hydrogenation of the liquefied oil obtained from the direct coal hydrogenation liquefaction reaction process;
③ hydrogenation process of oil product obtained from low temperature coal tar or distillate oil thereof or thermal processing process PU thereof, wherein the thermal processing process PU is selected from heating distillation process or coking process or thermal cracking process or shallow hydrogenation process or heavy oil catalytic cracking process;
④ hydrogenation process of oil product obtained from high temperature coal tar or distillate oil thereof or thermal processing process PU thereof, wherein the thermal processing process PU is selected from heating distillation process or coking process or thermal cracking process or shallow hydrogenation process or heavy oil catalytic cracking process;
⑤ hydrogenation process of heavy oil of shale oil or oil obtained from PU thermal processing process of shale oil, wherein the PU thermal processing process is selected from heating distillation process, coking process, thermal cracking process, shallow hydrogenation process, heavy oil catalytic cracking process or heavy oil catalytic cracking process;
⑥ hydrogenation process of oil product obtained by heavy oil thermal processing process PU of petroleum sand, wherein the thermal processing process PU is selected from heating distillation process, coking process, thermal cracking process, shallow hydrogenation process, heavy oil catalytic cracking process or heavy oil catalytic cracking process;
⑦ hydrogenation process of oil product obtained by the heavy oil thermal processing process PU, wherein the thermal processing process PU is selected from the heating distillation process, the coking process, the thermal cracking process, the shallow hydrogenation process, the heavy oil catalytic cracking process or the heavy oil catalytic cracking process;
⑧ other hydrocarbon oils with a weight content of aromatics higher than 45%, andor a weight content of gums higher than 15%, andor a weight content of asphaltenes higher than 5.0%.
8. The method of claim 1 or 2 or 3 or 4, wherein:
the first raw material RUF1 at least containing carbon element and hydrogen element is low-hydrogen content hydrocarbon, and is selected from one or more of the following materials:
① low temperature coal tar or distillate oil thereof or oil obtained by the thermal processing PU, wherein the thermal processing PU is selected from heating distillation process, coking process, thermal cracking process, shallow hydrogenation process, heavy oil catalytic cracking process or heavy oil catalytic cracking process;
② middle temperature coal tar or distillate oil thereof or oil obtained by the heat processing process PU, wherein the heat processing process PU is selected from heating distillation process or coking process or thermal cracking process or shallow hydrogenation process or heavy oil catalytic cracking process;
③ high temperature coal tar or distillate oil thereof or oil obtained by the thermal processing process PU, wherein the thermal processing process PU is selected from heating distillation process or coking process or thermal cracking process or shallow hydrogenation process or heavy oil catalytic cracking process;
④ coal liquefaction oil or distillate oil thereof obtained from coal liquefaction process or oil obtained from thermal processing process PU thereof, wherein the thermal processing process PU is selected from heating distillation process or coking process or thermal cracking process or shallow hydrogenation process or heavy oil catalytic cracking process;
⑤ shale oil or distillate oil thereof or oil obtained by the thermal processing process PU thereof, wherein the thermal processing process PU is selected from a heating distillation process, a coking process, a thermal cracking process, a shallow hydrogenation process, a heavy oil catalytic cracking process or a heavy oil catalytic cracking process;
⑥ petroleum sand-based heavy oil or oil obtained by the heat processing PU of the petroleum sand-based heavy oil, wherein the heat processing PU is selected from a heating distillation process, a coking process, a thermal cracking process, a shallow hydrogenation process, a heavy oil catalytic cracking process or a heavy oil catalytic cracking process;
⑦ thermal cracking of tar with petroleum-based wax oil;
⑧ oil obtained by the heavy oil thermal processing process PU, wherein the thermal processing process PU is selected from the heating distillation process, the coking process, the thermal cracking process, the light hydrogenation process, the heavy oil catalytic cracking process or the heavy oil catalytic cracking process;
⑨ the concentration of other polycyclic aromatic hydrocarbon is higher than 10%, and the total content of aromatic hydrocarbon is higher than 40%.
9. The method of claim 1 or 2 or 3 or 4, wherein:
③ in the process of washing and extracting WP, the acid water W01 to be washed is in contact separation with the extraction oil CY for 1-20 times;
④ the HU hydro-upgrading process is operated under the conditions of temperature 170-460 deg.C, pressure 4.0-28.0 MPa, and hydrogen/raw oil volume ratio 50-5000;
the extract oil CY obtained by separating the hydrogenation modified reaction product HUP mainly comprises hydrocarbon components with the conventional boiling point of 80-350 ℃.
10. The method of claim 1 or 2 or 3 or 4, wherein:
③ in the process of washing and extracting WP, the acid water W01 to be washed is in contact separation with the extraction oil CY for 1-20 times;
the extracted oil CY mainly comprises hydrocarbon components with the conventional boiling point of 80-350 ℃;
the operating conditions for the washing extraction process WP are: the pressure is 0.01-4.0 MPa, and the temperature is 10-75 ℃; defining the ratio of the weight flow of the extracted oil CY to the weight flow of the to-be-washed acidic water W01 as K900, wherein K900 is 0.01-0.5.
11. The method of claim 1 or 2 or 3 or 4, wherein:
③ in the process of washing and extracting WP, the acid water W01 to be washed is in contact separation with the extraction oil CY for 1-10 times;
the extracted oil CY mainly comprises hydrocarbon components with the conventional boiling point of 80-250 ℃;
the operating conditions for the washing extraction process WP are: the pressure is 0.1-1.0 MPa, and the temperature is 25-50 ℃; defining the ratio of the weight flow of the extracted oil CY to the weight flow of the to-be-washed acidic water W01 as K900, wherein the K900 is 0.05-0.20.
12. The method of claim 1 or 2 or 3 or 4, wherein:
① hydrocracking reaction process RU of hydrocarbon material, which is a suspension bed hydrocracking reaction process of processing coal and/or heavy oil using hydrogen-supplying solvent oil DS;
the hydrogen donor solvent oil DS is from a solvent oil hydrogenation stabilization reaction process DS-MR matched with the hydrocarbon material hydrogenation thermal cracking reaction process RU;
③ in the process of washing and extracting WP, the acid water W01 to be washed is contacted with the extracted oil CY at least once to be separated into washed acid water W05 and extracted rich oil WPY, and at least a part of the hydrocarbon oil with high aromaticity in the acid water W01 to be washed is transferred to the extracted rich oil WPY;
the extracted oil CY is hydrocarbons obtained in the separation and fractionation process of the DS-MRP product in the hydrogenation and stabilization reaction process of the solvent oil.
13. The method of claim 1 or 2 or 3 or 4, wherein:
① hydrocracking reaction process RU of hydrocarbon material, which is a hydrocracking reaction process of suspension bed of hydrogen-supplying solvent oil DS for processing coal and/or heavy oil;
the generated oil in the hydrogen material hydrogenation thermal cracking reaction process RU is subjected to RUP-FRAC fractionation to separate distillate RUP-FRAC-NY which mainly comprises hydrocarbon components with the conventional boiling point of 150-530 ℃; distilling distillate RUP-FRAC-NY to enter into a hydrogenation upgrading reaction process RDP;
③ in the process of washing and extracting WP, the acid water W01 to be washed is contacted with the extracted oil CY at least once to be separated into washed acid water W05 and extracted rich oil WPY, and at least a part of the hydrocarbon oil with high aromaticity in the acid water W01 to be washed is transferred to the extracted rich oil WPY;
the extracted oil CY is hydrocarbons obtained in the separation and fractionation process of a product RDP-P of the RDP in the hydrogenation upgrading reaction process.
14. The method of claim 1 or 2 or 3 or 4, wherein:
the extracted oil CY is rich absorption oil RS from the following de-oiling process X100 of a gas containing normal gaseous hydrocarbons and inferior normal liquid hydrocarbons;
the process X100 for the deoiling of a gas comprising normal gaseous hydrocarbons and inferior normal liquid hydrocarbons comprises the following steps:
① obtaining gas PUG and oil APY containing normal gas hydrocarbon and inferior normal liquid hydrocarbon SD in the heat processing process PU of the low hydrogen content hydrocarbon HDS;
a thermal processing process PU of the low hydrogen content hydrocarbon HDS, which is selected from a heating distillation process, a coking process, a thermal cracking process, a shallow hydrogenation process, a heavy oil catalytic cracking process or a heavy oil catalytic cracking process;
the poor-quality conventional liquid hydrocarbon SD refers to hydrocarbons which cause environmental pollution by direct combustion and contains at least one part of organic sulfur or at least one part of organic nitrogen or at least one part of aromatic hydrocarbon;
at least a part of oil APY enters the hydro-upgrading process HU of the step ② to be used as hydrogenation raw oil HU-F1;
② in the hydro-upgrading process HU, under the condition of hydrogen and hydrogenation catalyst HUC, the hydro-base oil HU-F1 completes hydro-upgrading reaction HUR and converts into hydro-upgrading reaction product HUP;
separating the hydro-upgrading reaction product HUP to obtain a hydrocarbon-containing oil stream HUPY, and feeding the stream HUPY to the absorption process ASU in the step ③ to be used AS absorption oil AS;
③ in the absorption process ASU, gas PUG and absorption oil AS are contacted and separated for at least one time and converted into deoiled gas PUG-D0 and rich absorption oil RS, and the rich absorption oil RS enters into the hydro-upgrading process HU and contacts with the hydrogenation catalyst HUC to carry out hydro-upgrading reaction.
15. The method of claim 1 or 2 or 3 or 4, wherein:
in the process of washing and extracting WP, the acid water W01 to be washed is contacted and separated with the extraction oil CY at least once to form washed acid water W05 and extracted rich oil WPY, and at least part of high-aromaticity hydrocarbon oil in the acid water W01 to be washed is transferred to the extracted rich oil WPY;
an extract rich oil WPY for use AS absorption oil AS in the following de-oiling process X100 of a gas containing normal gaseous hydrocarbons and inferior normal liquid hydrocarbons;
the process X100 for the deoiling of a gas comprising normal gaseous hydrocarbons and inferior normal liquid hydrocarbons comprises the following steps:
① obtaining gas PUG and oil APY containing normal gas hydrocarbon and inferior normal liquid hydrocarbon SD in the heat processing process PU of the low hydrogen content hydrocarbon HDS;
a thermal processing process PU of the low hydrogen content hydrocarbon HDS, which is selected from a heating distillation process, a coking process, a thermal cracking process, a shallow hydrogenation process, a heavy oil catalytic cracking process or a heavy oil catalytic cracking process;
the poor-quality conventional liquid hydrocarbon SD refers to hydrocarbons which cause environmental pollution by direct combustion and contains at least one part of organic sulfur or at least one part of organic nitrogen or at least one part of aromatic hydrocarbon;
at least a part of oil APY enters the hydro-upgrading process HU of the step ② to be used as hydrogenation raw oil HU-F1;
② in the hydro-upgrading process HU, under the condition of hydrogen and hydrogenation catalyst HUC, the hydro-base oil HU-F1 completes hydro-upgrading reaction HUR and converts into hydro-upgrading reaction product HUP;
separating the hydro-upgrading reaction product HUP to obtain a hydrocarbon-containing oil stream HUPY, and feeding the stream HUPY to the absorption process ASU in the step ③ to be used AS absorption oil AS;
③ in the absorption process ASU, gas PUG and absorption oil AS are contacted and separated for at least one time and converted into deoiled gas PUG-DO and rich absorption oil RS, and the rich absorption oil RS enters into the hydro-upgrading process HU to contact with the hydrogenation catalyst HUC for hydro-upgrading reaction.
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Application publication date: 20200317 |