CN114590853A - Method for treating waste water - Google Patents

Method for treating waste water Download PDF

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Publication number
CN114590853A
CN114590853A CN202011410853.4A CN202011410853A CN114590853A CN 114590853 A CN114590853 A CN 114590853A CN 202011410853 A CN202011410853 A CN 202011410853A CN 114590853 A CN114590853 A CN 114590853A
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Prior art keywords
catalytic cracking
wastewater
reaction
organic
weight
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CN202011410853.4A
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Chinese (zh)
Inventor
王伟
李华
林民
何驰剑
伍小驹
佘喜春
高计皂
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Hunan Changling Petrochemical Technology Development Co Ltd
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Hunan Changling Petrochemical Technology Development Co Ltd
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Priority to CN202011410853.4A priority Critical patent/CN114590853A/en
Publication of CN114590853A publication Critical patent/CN114590853A/en
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36Nature 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70Catalyst aspects
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/10Biological treatment of water, waste water, or sewage

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the field of wastewater treatment, in particular to a wastewater treatment method. The method comprises the following steps: in the presence of a catalytic cracking catalyst, wastewater containing organic matters and a catalytic cracking raw material are subjected to a catalytic cracking reaction. The method can omit a complex wastewater treatment process, but applies the wastewater to catalytic cracking reaction, saves the operation cost of catalytic cracking, and recycles organic matters in the wastewater; the method has simple operation, industrial feasibility and better economy.

Description

Method for treating waste water
Technical Field
The invention relates to the field of wastewater treatment, in particular to a wastewater treatment method.
Background
The sewage treatment adopts various necessary technologies and means to separate pollutants in the sewage so as to purify the water. The technology and means referred to here are the basic methods for sewage treatment.
Because the pollutants in the sewage are various, when a treatment method is selected, the pollutants with different properties can be removed by combining and using several methods, namely a physical treatment method, a chemical treatment method, a physicochemical treatment method and a biochemical treatment method, so as to achieve the aim of purification treatment.
The sewage treatment is divided into primary, secondary and tertiary treatment according to the treatment degree. The primary treatment mainly removes suspended solid pollutants in the sewage, and most of the physical treatment methods can only complete the primary treatment task. The removal rate of COD of the sewage after the first-stage treatment is only about 30 percent and far reaches the discharge standard. The secondary treatment mainly removes colloid dissolved organic substances in the sewage, adopts biological treatment mostly, and the COD removal rate can reach more than 90 percent, so that the organic pollutants in the sewage basically can reach or approach the discharge standard. The third treatment is to further treat refractory organic matters, nitrogen, phosphorus and other soluble inorganic matters capable of causing water eutrophication after the first and second treatments. Mainly adopts biological nitrogen and phosphorus removal method, coagulating sedimentation method, sand filtration method, activated carbon adsorption method, ion exchange method, reverse dialysis method and the like.
No matter the wastewater is treated by adopting a physical and chemical method or a biochemical method, the investment cost and the operation cost are increased, and the economy is not low.
Catalytic cracking units currently require the use of terminators, stripping steam and anti-coking steam to control the depth of the reaction; with the increasing weight of catalytic raw materials, the realization of high-temperature and short-time reaction technology is more and more important. The riser reactor injection terminator technology is a new technology similar to MTC (mixed temperature control) technology, and aims to independently control the oil agent mixed temperature at the bottom of a riser reactor and the reaction temperature at an outlet, improve the temperature distribution state of the riser and optimize the operation of the riser reactor. In order to inhibit the first reaction of hydrogen transfer and reduce the thermal cracking reaction, improve the yield of light oil and liquefied gas of heavy oil catalytic cracking, and reduce the yield of dry gas and coke, the reaction terminator technology has been widely applied. The catalytic cracker terminator may be water, light dirty oil, diesel oil, gasoline, etc., and according to the results of simulation, the effect is most excellent when the amount of the terminator injected (when oil is used as the terminator) is about 10% of the amount of the feedstock.
Disclosure of Invention
The invention aims to provide a wastewater treatment method, which can omit a complex wastewater treatment process, apply the wastewater to catalytic cracking reaction, save the operation cost of catalytic cracking and recycle organic matters in the wastewater. The method has simple operation, industrial feasibility and better economy.
The inventor of the invention breaks through the conventional thought of wastewater treatment, thinks about applying the wastewater containing organic matters to other processes, and finds that the wastewater containing organic matters is particularly suitable for a terminator of catalytic cracking reaction, thereby replacing the terminator originally used by the catalytic cracking reaction and reducing the reaction cost; and the wastewater containing organic matters can crack part or all of the organic matters in the wastewater into small molecules under the condition of catalytic cracking reaction, so that the organic matters can be directly discharged or collected and used together with products of the catalytic cracking reaction, thereby not only omitting a complicated wastewater treatment process, but also changing waste into valuable and having remarkable economical efficiency.
The invention provides a method for treating wastewater, wherein the method comprises the following steps: in the presence of a catalytic cracking catalyst, wastewater containing organic matters and a catalytic cracking raw material are subjected to a catalytic cracking reaction.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for treating wastewater, wherein the method comprises the following steps: in the presence of a catalytic cracking catalyst, carrying out catalytic cracking reaction on waste water containing organic matters and a catalytic cracking raw material.
In the present invention, the amount of the organic matter-containing wastewater is not particularly limited, and for example, the amount of the organic matter-containing wastewater may be 3.5 to 6 parts by weight, preferably 4 to 5.6 parts by weight, based on 100 parts by weight of the catalytic cracking feedstock.
The waste water of the invention is mainly used as a terminator in the catalytic cracking reaction so as to control the reaction depth of the catalytic cracking, therefore, when the supply amount of the waste water is not enough to meet the requirement, the waste water can be diluted by clean water for use, and can also be used together with other components used as the terminator.
The wastewater used in the present invention may be organic-containing wastewater produced by various chemical processes, such as one or more of an oxidation process, a reduction process, an acid-catalyzed process, and a base-catalyzed process.
In the present invention, the organic matter is various organic matters which are partially or completely cracked under the catalytic cracking condition, and generally hydrocarbon organic matters, oxygen-containing organic compounds, sulfur-containing organic compounds, nitrogen-containing organic compounds and other organic matters which can be partially or completely cracked under the catalytic cracking condition.
In the present invention, the concentration of the organic matter in the wastewater is not particularly limited, and wastewater having different organic matter components and different concentrations obtained from various chemical processes can be applied to the present invention, and the concentration of the organic matter in the wastewater is preferably 0.1 to 4% by weight, more preferably 1 to 3% by weight.
The method of the invention can be suitable for various catalytic cracking reactions, can well realize the full recycling of the wastewater under the catalysts and reaction conditions of various catalytic cracking reactions, and does not influence the catalytic cracking reaction result. In the present invention, the catalytic cracking catalyst may be any of various conventional catalytic cracking catalysts in the art, for example, the catalytic cracking catalyst may contain alumina, silica and rare earth oxide, and preferably, the content of the alumina is 45 to 55 wt%, the content of the silica is 40 to 50 wt% and the content of the rare earth oxide is 0.1 to 8 wt%, based on the total weight of the catalytic cracking catalyst.
The catalytic cracking catalyst may be used in an amount of 4 to 7 parts by weight, preferably 5 to 6 parts by weight, more preferably 5.2 to 5.5 parts by weight, based on 100 parts by weight of the catalytic cracking feedstock. In the present invention, the conditions of the catalytic cracking reaction preferably include: the reaction temperature is 440-560 ℃, preferably 460-530 ℃, the reaction pressure is 0.1-0.4MPa, preferably 0.2-0.36MPa, and the residence time is 4-7s, preferably 5-6 s.
In the present invention, the organic matter-containing wastewater may be added together after being mixed with the catalytic cracking feedstock, or may be fed from a terminator inlet, for example, when a fluidized bed reactor is used, the terminator inlet is usually located at the middle end of the fluidized bed reactor. The organic-containing wastewater may be fed after the start of the reaction or before the start of the reaction.
In the invention, the organic matters in the waste water containing the organic matters are partially or completely cracked into small molecules under the reaction condition of catalytic cracking, and the small molecules obtained by cracking are usually one or more of hydrocarbons, sulfur-containing compounds, carbon monoxide, carbon dioxide, hydrogen, nitrogen and nitrogen-containing compounds, wherein the sulfur-containing compounds are usually one or more of hydrogen sulfide, sulfur dioxide and sulfur trioxide, the nitrogen-containing compounds are usually one or more of nitrogen, dinitrogen pentoxide and nitrogen monoxide, and the hydrocarbons are usually one or more of low-carbon hydrocarbons such as ethylene, ethane, propylene, propane and the like.
The present invention will be described in detail below by way of examples. In the following examples and comparative examples, the organic content (% by weight) was measured by a gas chromatograph (manufacturer agilent, brand 7820); organic matter conversion (%) - (amount of inlet organic matter-amount of outlet organic matter) ÷ amount of inlet organic matter × 100%. The activity of the catalyst is determined by collecting a catalyst sample, carrying out a catalytic cracking reaction of the light diesel oil in a micro-reaction evaluation device, and detecting the quantity of the import and export light diesel oil, wherein the activity (%) of the catalyst is divided by the weight of the raw material light diesel oil-the weight of the light diesel oil in the product, and the weight of the raw material light diesel oil is multiplied by 100%.
Example 1
A catalytic cracking test was carried out in a fluidized bed reactor, in which organic matter-containing wastewater (referred to as "feed water" for short, the content of organic matter is shown in Table 1) obtained by mixing propylene glycol monomethyl ether-extracted wastewater from a propylene-to-propylene oxide plant with alcohol-containing wastewater was fed from a terminator inlet at the middle of the fluidized bed reactor, and the organic matter-containing wastewater and feed oil (the density at 20 ℃ C. was 0.92g cm.)-3The feed ratio of distillation range IBP/EBP is 35-500 ℃ C. is 4.5: 100, the catalyst is a DFC-1 catalyst (wherein the content of alumina is 47 wt%, the content of silica is 49 wt%, and the content of rare earth oxide is 3 wt%) commercially available from chang division, a petrochemical catalyst company, and the weight ratio of the catalyst to the feed oil is 5.3: 100, the conditions of catalytic cracking comprise: the reaction temperature was 510 deg.C, the reaction pressure was 0.28MPa, and the residence time was 5.2 s.
The organic content of the aqueous phase liquid (referred to as "effluent" for short) separated by condensation after catalytic cracking was measured, and the conversion of the organic was obtained by calculation, and the results are shown in table 1.
The activity of the catalyst before and after the catalytic cracking reaction was measured, and the results are shown in table 1.
Comparative example 1
The procedure is as in example 1, except that the waste water containing organic matter is replaced with clean water of the same quality.
The organic content of the aqueous liquid (referred to as "effluent" for short) separated by condensation after catalytic cracking was measured, and the results are shown in table 1.
The activity of the catalyst before and after the catalytic cracking reaction was measured, and the results are shown in table 1.
Comparative example 2
The procedure is as in example 1, except that the organic-containing wastewater is replaced with light dirty oil of the same mass (density at 20 ℃ C. of 0.75 g-cm)-3The distillation range IBP/EBP is 40-200 deg.C.
The activity of the catalyst before and after the catalytic cracking reaction was measured, and the results are shown in table 1.
Example 2
A catalytic cracking test was carried out in a fluidized bed reactor, and organic matter-containing wastewater (components shown in Table 1) obtained by mixing wastewater from a propylene-to-propylene oxide plant without propylene glycol monomethyl ether extraction with alcohol-containing wastewater was fed from a terminator inlet at the middle of the fluidized bed reactor, wherein the feed ratio of the organic matter-containing wastewater to the feedstock oil (same as example 1) was 4: 100, the catalyst is a catalyst with the trade name of CGP-C (wherein, the content of alumina is 51 wt%, the content of silica is 47 wt%, and the content of rare earth oxide is 1 wt%) which is commercially available from Changjingtong division of China petrochemical catalyst company, and the weight ratio of the catalyst to the raw oil is 5: 100, the conditions of catalytic cracking comprise: the reaction temperature is 530 ℃, the reaction pressure is 0.36MPa, and the retention time is 5 s.
The organic content of the aqueous phase liquid (referred to as "effluent" for short) separated by condensation after catalytic cracking was measured, and the conversion of the organic was obtained by calculation, and the results are shown in table 1.
The activity of the catalyst before and after the catalytic cracking reaction was measured, and the results are shown in table 1.
Example 3
In a catalytic cracking test in a fluidized bed reactor, organic matter-containing wastewater (components shown in table 1) obtained by mixing wastewater from a propylene oxide production apparatus not extracting propylene glycol monomethyl ether with alcohol-containing wastewater was fed from a terminator inlet at the lower part of the fluidized bed reactor, and the feed ratio of the organic matter-containing wastewater to the feedstock oil (same as example 1) was 5.6: 100, the catalyst is a CDOS catalyst (wherein the content of alumina is 50 wt%, the content of silica is 44 wt%, and the content of rare earth oxide is 5 wt%) commercially available from chang mountain division of petrochemical catalyst company, and the weight ratio of the catalyst to the feedstock oil is 6: 100, the conditions of catalytic cracking comprise: the reaction temperature is 460 ℃, the reaction pressure is 0.2MPa, and the retention time is 6 s.
The organic content of the aqueous phase liquid (referred to as "effluent" for short) separated by condensation after catalytic cracking was measured, and the conversion of the organic was obtained by calculation, and the results are shown in table 1.
The activity of the catalyst before and after the catalytic cracking reaction was measured, and the results are shown in table 1.
TABLE 1
Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2
Influent organic content/weight% 1.53 3.76 3.76 0 -
The content of organic matters in effluent water per weight percent 0.10 0.13 0.08 0.13 -
Organic matter conversion/% 93.46 96.54 98.87 - -
Pre reaction catalyst activity/%) 55.53 56.45 58.23 59.32 56.54
Post-reaction catalyst activity/%) 55.52 56.45 58.22 59.22 56.52
As can be seen from table 1, when the wastewater containing organic substances is applied to catalytic cracking reaction according to the method of the present invention, the content of organic substances in the obtained effluent can be less than 0.15 wt%, and the conversion rate of organic substances can be more than 93%.
And the activity of the catalyst before and after the reaction is compared to show that the activity of the catalyst before and after the reaction is not obviously changed, which proves that the method of the invention has no influence on the activity of the catalyst, namely the method of the invention does not influence the original catalytic cracking reaction and can realize good reaction activity and reaction depth of the catalytic cracking reaction.
Further, the content (wt%) of components in a gas phase obtained by the catalytic cracking reaction was measured by a gas chromatograph (manufacturer's Agilent, brand 7820), and the gas composition was shown in Table 2, taking ethylene, propylene and carbon monoxide as main components, and the gas obtained in example 1 as an example. Wherein, C2 Is referred to as ethylene, C3 0Is propane, C3 Refers to propylene, n-C4 0Means n-butane, n-C4 Is n-butene, i-C4 Is isobutylene, t-C4 Is intended to mean fumaric acid, C-C4 Is maleic acid, i-C5 0Is isopentane, n-C5 0Is n-pentane, C5 +C6 0Refers to carbon penta-and hexa-olefins.
TABLE 2
Figure BDA0002815198330000071
As can be seen from table 2, the organic matter in the waste water containing organic matter can be partially or completely cracked into small molecules under the reaction conditions of catalytic cracking, and thus the small molecules enter the gas phase to be recycled. That is, the method of the invention not only saves the complex wastewater treatment process, but also fully recycles the organic matters in the wastewater, thus being an energy-saving, environment-friendly and sustainable development method.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention. It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition. In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (9)

1. A method of wastewater treatment, the method comprising: in the presence of a catalytic cracking catalyst, wastewater containing organic matters and a catalytic cracking raw material are subjected to a catalytic cracking reaction.
2. The method according to claim 1, wherein the organic matter-containing wastewater is used in an amount of 3.5 to 6 parts by weight based on 100 parts by weight of the catalytic cracking feedstock.
3. The method according to claim 2, wherein the organic matter-containing wastewater is used in an amount of 4 to 5.6 parts by weight based on 100 parts by weight of the catalytic cracking feedstock.
4. The method of any one of claims 1-3, wherein the organic is one or more of a hydrocarbon organic, an oxygen-containing organic compound, a sulfur-containing organic compound, and a nitrogen-containing organic compound.
5. The method according to any one of claims 1 to 3, wherein the concentration of the organic matter in the organic matter-containing wastewater is 0.1 to 4% by weight.
6. The method of any one of claims 1-5, wherein the wastewater is an organic-containing wastewater produced by a chemical process, the chemical process being one or more of an oxidation process, a reduction process, an acid-catalyzed process, and a base-catalyzed process.
7. The process as claimed in claim 1, wherein the catalytic cracking catalyst is used in an amount of 4 to 7 parts by weight based on 100 parts by weight of the catalytic cracking feedstock.
8. The process of claim 1, wherein the conditions of the catalytic cracking reaction comprise: the reaction temperature is 440-560 ℃, the reaction pressure is 0.1-0.4MPa, and the retention time is 4-7 s.
9. The process of claim 8, wherein the conditions of the catalytic cracking reaction comprise: the reaction temperature is 460 ℃ and 530 ℃, the reaction pressure is 0.2-0.36MPa, and the retention time is 5-6 s.
CN202011410853.4A 2020-12-03 2020-12-03 Method for treating waste water Pending CN114590853A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107010709A (en) * 2017-05-27 2017-08-04 南京工业大学 The purification method of high-concentration phenolic wastewater during a kind of neighbour/Process of Hydroquinone Production
CN107010761A (en) * 2017-05-27 2017-08-04 南京工业大学 A kind of combined purifying method of neighbour/4-chloro-benzaldehyde distillation residual liquid and technique waste water
CN107188329A (en) * 2017-05-27 2017-09-22 南京工业大学 A kind of combined purifying method of technique waste water and distillation residual liquid in Industrial Process of Aniline
CN107267211A (en) * 2016-04-06 2017-10-20 中国石油化工股份有限公司 The processing method and system of a kind of inferior feedstock oil

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107267211A (en) * 2016-04-06 2017-10-20 中国石油化工股份有限公司 The processing method and system of a kind of inferior feedstock oil
CN107010709A (en) * 2017-05-27 2017-08-04 南京工业大学 The purification method of high-concentration phenolic wastewater during a kind of neighbour/Process of Hydroquinone Production
CN107010761A (en) * 2017-05-27 2017-08-04 南京工业大学 A kind of combined purifying method of neighbour/4-chloro-benzaldehyde distillation residual liquid and technique waste water
CN107188329A (en) * 2017-05-27 2017-09-22 南京工业大学 A kind of combined purifying method of technique waste water and distillation residual liquid in Industrial Process of Aniline

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