CN109133405B - Method for purifying sulfur-containing sewage of delayed coking - Google Patents

Method for purifying sulfur-containing sewage of delayed coking Download PDF

Info

Publication number
CN109133405B
CN109133405B CN201710463172.6A CN201710463172A CN109133405B CN 109133405 B CN109133405 B CN 109133405B CN 201710463172 A CN201710463172 A CN 201710463172A CN 109133405 B CN109133405 B CN 109133405B
Authority
CN
China
Prior art keywords
sulfur
delayed coking
containing sewage
sewage
polyether
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710463172.6A
Other languages
Chinese (zh)
Other versions
CN109133405A (en
Inventor
于丽
王振宇
沈明欢
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN201710463172.6A priority Critical patent/CN109133405B/en
Publication of CN109133405A publication Critical patent/CN109133405A/en
Application granted granted Critical
Publication of CN109133405B publication Critical patent/CN109133405B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C02F1/766—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens by means of halogens other than chlorine or of halogenated compounds containing halogen other than chlorine
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/101—Sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil
    • C02F2101/325—Emulsions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/40—Organic compounds containing sulfur
    • 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)
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/02—Temperature
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Activated Sludge Processes (AREA)

Abstract

The invention relates to the technical field of industrial sewage treatment, and discloses a method for purifying delayed coking sulfur-containing sewage, which comprises the following steps: firstly, the delayed coking sulfur-containing sewage is contacted with acid or weak oxidant, then alkyl phenolic resin polyether is added into the system, and demulsification separation treatment is carried out; or adding alkyl phenolic resin polyether into the delayed coking sulfur-containing sewage, then contacting the obtained system with acid or weak oxidant, and performing demulsification separation treatment. The method is suitable for purifying the delayed coking sulfur-containing sewage, and has the advantages of simple operation, low cost and good water purifying effect.

Description

Method for purifying sulfur-containing sewage of delayed coking
Technical Field
The invention relates to the technical field of industrial sewage treatment, in particular to a method for purifying and treating sulfur-containing sewage at the top of a delayed coking tower in an oil refinery.
Background
The delayed coking process is one of the main processes for further processing heavy oil, vacuum residuum is one of the main raw materials for processing the heavy oil, most of sulfur in crude oil is enriched in the residuum, so delayed coking sewage is one of the main sewage sources of refineries, wherein the oil-containing and sulfur-containing waste water accounts for more than 90% of the total delayed coking sewage, and the sewage not only contains dirty oil, heterocyclic compounds with sulfur and the like, but also is rich in various gases with foul smell. Under the background of the increasingly strict requirements on environmental protection and the increasingly deteriorated crude oil, how to treat the pollution problem generated by the delayed coking wastewater becomes the difficult problem of each large refinery, and the concern of each refinery is increasing.
The delayed coking material is vacuum residuum from upstream atmospheric and vacuum distillation equipment, the sulfur content and other impurity content in the vacuum residuum are high, so that the oil gas at the top of coking fractionating tower is settled by means of oil-water separator, the discharged sulfur-containing sewage is milk-white, contains lots of gasoline fractions, and has the phenomenon of serious emulsification of oil and water, and the water layer still is yellow and opaque, and the coking sewage contains coke powder and nitride, but it is not the main reason for emulsification of oil and water, and the main reason for said phenomenon is that these sulfur-containing sewage contains lots of various sulfur-containing compounds, and these sulfur compounds include carbon disulfide, thiols, thiophene, thioether and polysulfide, etc. besides hydrogen sulfide, and the existence of these sulfur-containing compounds can make oil-water emulsification serious.
At present, foreign documents on demulsification of oil-in-water emulsions are more, but patent documents on demulsification and oil removal of sewage at the top of a coking tower are not found. The domestic patent application related to delayed coking wastewater treatment mainly focuses on the aspect of a coking wastewater treatment device, and mainly comprises filtration methods such as a filter, cyclone and multistage sedimentation, and the used materials mainly comprise metal materials, high polymer materials, ceramics and the like.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a method for purifying delayed coking sulfur-containing sewage, which is suitable for purifying the delayed coking sulfur-containing sewage, and has the advantages of simple operation, low cost and good water purification effect.
In order to achieve the above object, the present invention provides a method for purifying sulfur-containing sewage of delayed coking, comprising: firstly, the delayed coking sulfur-containing sewage is contacted with acid or weak oxidant, then alkyl phenolic resin polyether is added into the system, and demulsification separation treatment is carried out; or
Firstly, adding alkyl phenolic resin polyether into the delayed coking sulfur-containing sewage, then contacting the obtained system with acid or weak oxidant, and performing demulsification separation treatment.
The method can perform good purification treatment on the delayed coking sulfur-containing sewage (especially the sulfur-containing sewage at the top of a delayed coking tower of an oil refinery), and has the advantages of simple operation, low cost and good water purification effect by a mode of firstly contacting the delayed coking sulfur-containing sewage with an acid or a weak oxidant, then adding alkyl phenolic resin polyether into a system, and performing demulsification separation treatment or firstly adding alkyl phenolic resin polyether into the delayed coking sulfur-containing sewage, then contacting the obtained system with the acid or the weak oxidant, and performing demulsification separation treatment.
Detailed Description
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.
In one aspect, the present invention provides a method for purifying delayed coking wastewater containing sulfur, comprising: firstly, the delayed coking sulfur-containing sewage is contacted with acid or weak oxidant, then alkyl phenolic resin polyether is added into the system, and demulsification separation treatment is carried out (namely, demulsification separation of oil-water emulsion is realized).
In the method of the present invention, when the delayed coking sulfur-containing sewage is contacted with an acid or a weak oxidizing agent, the delayed coking sulfur-containing sewage reacts with the acid or is oxidized by the weak oxidizing agent in a short time, and since the acid is corrosive, the delayed coking sulfur-containing sewage is preferably contacted with the weak oxidizing agent before the alkylphenol aldehyde resin polyether is added.
In the method of the present invention, in order to further improve the treatment effect of the delayed coking sulfur-containing sewage, the amount of the acid is preferably controlled so that the pH of the delayed coking sulfur-containing sewage is 4 to 7.5, more preferably 5 to 7.
Among them, the acid may be an inorganic acid commonly used in the art, and preferably, the acid is at least one of hydrochloric acid, sulfuric acid, and phosphoric acid, and more preferably hydrochloric acid.
It will be understood by those skilled in the art that after contacting the delayed coking sour water with the acid or mild oxidant, the system is mixed to form a homogeneous emulsion, which may be at ambient temperature, for example, 15-35 ℃.
In the method of the present invention, in order to further improve the treatment effect of the delayed coking sulfur-containing sewage, the amount of the weak oxidizing agent is preferably controlled so that the sulfur-containing compounds in the delayed coking sulfur-containing sewage are completely oxidized. Specific types of sulfur-containing compounds in the delayed coking sour water are well known to those skilled in the art, and may include, for example, hydrogen sulfide, carbon disulfide, thiols, thiophenes, thioethers, polysulfides, and the like.
Among them, preferably, the weak oxidizing agent is at least one of air, iodine, iron oxide and manganese dioxide, and since other oxidizing agents have little difference in effect compared with air but additionally introduce other impurities, it is further preferable that the weak oxidizing agent is air. Wherein, when the weak oxidant is air, the color of the delayed coking sulfur-containing sewage can be oxidized from a yellow opaque state to an off-white opaque state through the air. When the weak oxidizing agent is at least one of iodine, ferric oxide and manganese dioxide, the specific weak oxidizing agent used for completely oxidizing the sulfur-containing compounds can be determined by the type and content of the sulfur-containing compounds in the delayed coking sulfur-containing sewage.
In the method of the present invention, in order to further improve the effect of treating the delayed coking sulfur-containing sewage, it is preferable that the alkylphenol aldehyde resin polyether has a structural formula of H (C)2H4O)a(C3H6O)b(C2H4O)cO-(C6H4-CH2-)10Wherein (a + c)/b is 0.8 to 1, and more preferably 0.84 to 0.95.
Among them, in order to further improve the effect of treating the delayed coking sulfur-containing sewage, the alkylphenol aldehyde resin polyether is preferably added in an amount of 5 to 200ppm, more preferably 20 to 100 ppm.
It will be understood by those skilled in the art that after adding the alkylphenol-formaldehyde resin polyether to the system, the system is thoroughly mixed and subjected to a demulsification separation treatment, and the temperature of adding the alkylphenol-formaldehyde resin polyether may be normal temperature, for example, 15-35 ℃.
In another aspect, the present invention provides a method for purifying sulfur-containing sewage from delayed coking, the method comprising: firstly, adding alkyl phenolic resin polyether into the delayed coking sulfur-containing sewage, then contacting the obtained system with acid or weak oxidant, and performing demulsification separation treatment (namely, realizing demulsification separation of oil-water emulsion).
In the method of the present invention, in order to further improve the effect of treating the delayed coking sulfur-containing sewage, it is preferable that the alkylphenol aldehyde resin polyether has a structural formula of H (C)2H4O)a(C3H6O)b(C2H4O)cO-(C6H4-CH2-)10Wherein (a + c)/b is 0.8 to 1, and more preferably 0.84 to 0.95.
Among them, in order to further improve the effect of treating the delayed coking sulfur-containing sewage, the alkylphenol aldehyde resin polyether is preferably added in an amount of 5 to 200ppm, more preferably 20 to 100 ppm.
Wherein, the temperature for adding the alkyl phenolic resin polyether into the delayed coking sulfur-containing sewage can be normal temperature, such as 15-35 ℃. Adding alkyl phenolic resin polyether into the delayed coking sulfur-containing sewage, and then fully mixing to obtain a mixed system.
In the method of the present invention, when the obtained system is contacted with an acid or a weak oxidizing agent, the delayed coking sulfur-containing wastewater reacts with the acid or is oxidized by the weak oxidizing agent in a short time, and since the acid is corrosive, it is preferable that the obtained system is contacted with the weak oxidizing agent after the alkylphenol aldehyde resin polyether is added.
In the method of the present invention, in order to further improve the treatment effect of the delayed coking sulfur-containing sewage, the amount of the acid is preferably controlled so that the pH of the delayed coking sulfur-containing sewage in the system is 4 to 7.5, and more preferably 5 to 7.
Among them, the acid may be an inorganic acid commonly used in the art, and preferably, the acid is at least one of hydrochloric acid, sulfuric acid, and phosphoric acid, and more preferably hydrochloric acid.
Wherein, after contacting with the acid or the weak oxidizing agent, the system is mixed into a uniform emulsion, and the contacting temperature can be normal temperature, such as 15-35 ℃.
In the method of the present invention, in order to further improve the treatment effect of the delayed coking sulfur-containing sewage, the amount of the weak oxidizing agent is preferably controlled so that the sulfur-containing compounds in the delayed coking sulfur-containing sewage are completely oxidized. Specific types of sulfur-containing compounds in the delayed coking sour water are well known to those skilled in the art, and may include, for example, hydrogen sulfide, carbon disulfide, thiols, thiophenes, thioethers, polysulfides, and the like.
Among them, preferably, the weak oxidizing agent is at least one of air, iodine, iron oxide and manganese dioxide, and since other oxidizing agents have little difference in effect compared with air but additionally introduce other impurities, it is further preferable that the weak oxidizing agent is air. Wherein, when the weak oxidant is air, the color of the delayed coking sulfur-containing sewage can be oxidized from a yellow opaque state to an off-white opaque state through the air. When the weak oxidizing agent is at least one of iodine, ferric oxide and manganese dioxide, the specific weak oxidizing agent used for completely oxidizing the sulfur-containing compounds can be determined by the type and content of the sulfur-containing compounds in the delayed coking sulfur-containing sewage.
In the above two methods of the present invention, in order to further improve the treatment effect of the delayed coking sulfur-containing sewage, the demulsification separation treatment conditions preferably include: the temperature is 10 to 60 ℃ and more preferably 40 to 50 ℃.
In the above two methods of the present invention, preferably, the conditions of the demulsification and separation treatment further include: the time is 10min to 6h, and more preferably 50 to 90 min.
Wherein, the demulsification separation treatment mode can be standing sedimentation treatment.
In the two methods, the pH value of the delayed coking sulfur-containing sewage is 8-10, the oil content in the delayed coking sulfur-containing sewage is 5000-40000mg/L, the sulfur-containing compound content is 10000-20000mg/L, and the ammonia nitrogen content is 1000-5000 mg/L. The delayed coking sulfur-containing sewage may be fresh delayed coking sulfur-containing sewage at the time of treatment.
In order to further improve the treatment effect of the sulfur-containing sewage of delayed coking, in the two methods, the method of the invention preferably comprises the following steps: firstly, the delayed coking sulfur-containing sewage is contacted with acid or weak oxidant, then alkyl phenolic resin polyether is added into the system, and demulsification separation treatment is carried out.
In the method of the present invention, the wastewater to which each water purifying agent (including an acid or a weak oxidizing agent and alkylphenol-formaldehyde resin polyether) is added may be scanned, and the water purifying effect of the method of the present invention may be evaluated based on the transmitted light intensity of the wastewater. Specifically, the method for scanning the sewage may include: scanning with 880nm near infrared light from the bottom of the sample upwards along the sample testing chamber using a Turbiscan emulsion stability analyzer (available from Del, Inc. under the model Lab Expert), collecting transmitted light intensity data every 40 μm height, wherein the scanning curve shows the variation of transmitted light intensity with the sample height, reflecting the microscopic change in the emulsion, and recording the maximum transmitted light intensity collected at different scanning times as the transmitted light intensity data at the time. Wherein the temperature during scanning is the same as the demulsification and separation temperature of the oil-water emulsion, namely the scanning temperature is 10-60 ℃, and preferably 40-50 ℃; the scanning time corresponds to the time of the demulsification separation treatment.
Examples
The present invention will be described in detail below by way of examples, but the present invention is not limited thereto. In the following examples and comparative examples, unless otherwise specified, the respective methods used are conventional in the art, and the respective reagents and materials used are commercially available.
The alkylphenol formaldehyde polyethers with different (a + c)/b ratios are available from Shandong Binshiji group, Inc., wherein the alkylphenol formaldehyde polyethers with a + c-12, b-13 have the designation BSQ-1, the alkylphenol formaldehyde polyethers with a + c-12, b-15 have the designation BSQ-2, the alkylphenol formaldehyde polyethers with a + c-12, b-12 have the designation BSQ-3, the alkylphenol formaldehyde polyethers with a + c-11, b-13 have the designation BSQ-4, and the alkylphenol formaldehyde polyethers with a + c-13, b-13 have the designation BSQ-5.
The transmitted light intensity of the wastewater was measured using a Turbiscan emulsion stability analyzer (available from dell, model Lab Expert).
The fresh delayed coking tower top sulfur-containing sewage used in each example has a pH value of 9, the oil content of the delayed coking sulfur-containing sewage is 20000mg/L, the sulfur-containing compound content is 15000mg/L, and the ammonia nitrogen content is 3000 mg/L.
Example 1
This example is intended to illustrate the process for the purification of sulfur-containing wastewater from delayed coking according to the invention, wherein the acid species used in the different experiments are different.
Adding hydrochloric acid, sulfuric acid or phosphoric acid into sulfur-containing sewage at the top of fresh delayed coking tower, adjusting pH to 7, and homogenizing with homogenizer at mixing intensity of 2 × 104Mixing sewage into uniform emulsion under the condition of mixing time of 2min, respectively pouring the emulsion into sample bottles for scanning, adding 100ppm of alkyl phenolic resin polyether, wherein a + c is 12, b is 13, tightly covering the sample bottles, manually mixing the emulsion for 30 times, putting the mixture into an instrument, setting scanning start time, scanning frequency (scanning once every 20 min) and total scanning time at the temperature of 50 ℃, starting automatic detection on water samples in the sample bottles by the instrument, evaluating the quality of different conditions or different medicaments according to the intensity and weakness of transmitted light corresponding to the clear and turbid of water, and comparing the maximum transmitted light intensity values at the scanning time of 20min, 40min and 60min in all experiments. The results are shown in Table 1, blank for acid-free + alkyl phenol-formaldehyde polyether + demulsification of oil-water emulsion (i.e., blank for same conditions except for no acid).
TABLE 1
Figure BDA0001325301170000071
Figure BDA0001325301170000081
As can be seen from the data in Table 1, the purification effect of the wastewater can be further improved when the acid is hydrochloric acid.
Example 2
This example is intended to illustrate the process for the purification of sulfur-containing sewage from delayed coking according to the invention, in which the amount of acid added varies from experiment to experiment.
The procedure of example 1 was followed except that hydrochloric acid was added to each of the sulfur-containing wastewaters from the top of the fresh delayed coking drum to adjust the pH of the wastewaters to 4, 5, 6, 7 and 7.5 (corresponding to samples 1 to 5 in Table 2, respectively). The results are shown in Table 2, blank for demulsification of emulsions in water and oil without acid, with alkyl phenol-formaldehyde polyether, and with oil-water emulsion (i.e., blank for the same conditions except for the absence of acid).
TABLE 2
Figure BDA0001325301170000082
As can be seen from the data in Table 2, the amount of the acid used was controlled so that the effect of purifying the sulfur-containing wastewater could be further improved when the pH of the wastewater was 5 to 7.
Example 3
This example is intended to illustrate the process for the purification of sulfur-containing wastewater from delayed coking according to the invention, in which the wastewater is brought into contact with a weak oxidizing agent in different experiments and the type of weak oxidizing agent used is different.
Following the procedure of example 1 except that the wastewater was replaced with acid and the process and conditions were the same as in example 1 except that the wastewater was contacted with a weak oxidizing agent, fresh sulfur-containing wastewater at the top of the delayed coking tower was allowed to stand for a period of time and was allowed to stand closed for a period of time until the wastewater changed from yellow opaque to off-white opaque (as sample 1) in color in order to prevent the odor from polluting the atmosphere; iodine, iron oxide or manganese dioxide was added to the fresh delayed coking overhead sulfur-containing wastewater, respectively, so that the sulfur-containing compounds in the wastewater were just completely oxidized, and the wastewater to which iodine, iron oxide or manganese dioxide was added corresponded to samples 2 to 4 in table 3, respectively. The results are shown in Table 3, blank is not oxidized + adding alkyl phenol-formaldehyde polyether + demulsifying and separating the oil-water emulsion (i.e., blank is the same except that no oxidation treatment is performed).
TABLE 3
Figure BDA0001325301170000091
It can be seen from the data in table 3 that when the weak oxidant is air, the purification effect of sewage can be further improved, no other impurities are introduced, and the cost can be saved.
Example 4
This example illustrates the process for the purification of delayed coking sour water according to the invention, wherein the alkylphenol-formaldehyde resin polyethers used in the different experiments differ.
The procedure of sample 1 in example 3 was followed except that the alkylphenol aldehyde resin polyethers used in samples 1 to 5 in example 4 were as follows: sample 1 had 12 and 13 alkyl phenol-formaldehyde resin polyethers a + c, 12 and 15 alkyl phenol-formaldehyde resin polyethers a + c, 12 and 12 b, sample 3 had 12 alkyl phenol-formaldehyde resin polyethers a + c, 11 and 13 alkyl phenol-formaldehyde resin polyethers a + c, 13 and 13 b, respectively, wherein the amount of each alkyl phenol-formaldehyde resin polyether added was 100 ppm. The results are shown in Table 4, blank oxidation + no alkylphenol polyethers added + demulsification separation of oil-water emulsions (i.e., blank conditions are the same except that no alkylphenol polyethers are added).
TABLE 4
Figure BDA0001325301170000101
As can be seen from the data in Table 4, the alkylphenol resin polyether H (C) used2H4O)a(C3H6O)b(C2H4O)cO-(C6H4-CH2-)10In (a + c)/b is 0.84 to 0.95, the effect of purifying the waste water can be further improved.
Example 5
This example illustrates the process for the purification of delayed coking sour water according to the invention, wherein the amount of alkylphenol-formaldehyde resin polyether added varies from experiment to experiment.
The procedure of sample 1 in example 3 was followed except that the alkylphenol-formaldehyde resin polyethers used in example 5 were each a + c-12 and b-13, and were added in amounts of 0ppm, 5ppm, 10ppm, 20ppm, 50ppm, 100ppm, 150ppm, and 200ppm, respectively. The results are shown in Table 5.
TABLE 5
Figure BDA0001325301170000102
Figure BDA0001325301170000111
As can be seen from the data in Table 5, when the addition amount of the alkylphenol formaldehyde resin polyether is 20-100ppm, not only the sewage purification effect can be further improved, but also the cost can be saved.
Example 6
This example illustrates the process for the purification of delayed coking sour water of the present invention wherein the temperature at which the oil and water emulsion is broken and separated is varied in different experiments.
The procedure of sample 1 in example 3 was followed except that the scanning temperatures in example 6 were 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃ and 60 ℃, respectively. The results are shown in Table 6.
TABLE 6
Figure BDA0001325301170000112
As can be seen from the data in Table 6, the suitable temperature for demulsification separation is 40-50 deg.C.
Example 7
According to the method of example 1, which is different from the method of adding alkylphenol-formaldehyde resin polyether and then adding acid and demulsifying and separating the oil-water emulsion, the method comprises the following steps: adding 100ppm of alkyl phenolic resin polyether into sulfur-containing sewage at the top of a fresh delayed coking tower, wherein a + c is 12 and b is 13, fully mixing, adding hydrochloric acid, and adjusting the pH value of the sewageAdjusting to 7, mixing with a homogenizer at a mixing intensity of 2 × 104Mixing the sewage into uniform emulsion for 2min, pouring the emulsion into a sample bottle for scanning, tightly covering the sample bottle, putting the sample bottle into an instrument, and measuring the transmitted light intensity value at the temperature of 50 ℃. The results are shown in Table 7.
Example 8
According to the method of example 3, which is different from the method of adding alkylphenol-formaldehyde resin polyether, oxidizing and demulsifying and separating the oil-water emulsion, the method comprises the following steps: adding 100ppm of alkyl phenolic resin polyether into sulfur-containing sewage at the top of a fresh delayed coking tower, wherein a + c is 12 and b is 13, fully mixing, then sealing and placing for a period of time until the color of the sewage is changed from yellow opaque to grey opaque, and mixing with a homogenizer at a mixing intensity of 2 multiplied by 104Mixing the sewage into uniform emulsion for 2min, pouring the emulsion into a sample bottle for scanning, tightly covering the sample bottle, putting the sample bottle into an instrument, and measuring the transmitted light intensity value at the temperature of 50 ℃. The results are shown in Table 7.
Comparative example 1
The procedure of example 1 was followed as in example 3 except that the alkylphenol resin polyether was replaced with an equal amount of linear polyether (available from Shandong Binshi group, LLC under the designation SP-169). The results are shown in Table 7.
TABLE 7
Figure BDA0001325301170000121
It can be seen from the data in table 7 that the purification treatment is performed by the method of contacting the sulfur-containing wastewater of delayed coking with acid or weak oxidant, adding alkyl phenolic resin polyether into the system, and performing demulsification separation treatment, so that the purification effect of the wastewater can be further improved, and the method is simpler and more convenient and is easy to operate.
As can be seen from the results in tables 1-7, the method for purifying the delayed coking sulfur-containing sewage has the advantages of simple operation, low cost and good water purification effect.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (12)

1. A method for purifying sulfur-containing sewage of delayed coking is characterized by comprising the following steps: firstly, the delayed coking sulfur-containing sewage is contacted with a weak oxidant, then alkyl phenolic resin polyether is added into the system, and demulsification separation treatment is carried out; or
Firstly, adding alkyl phenolic resin polyether into the delayed coking sulfur-containing sewage, then contacting the obtained system with a weak oxidant, performing demulsification separation treatment,
wherein the pH value of the delayed coking sulfur-containing sewage is 8-10, the oil content in the delayed coking sulfur-containing sewage is 5000-40000mg/L, the sulfur-containing compound content is 10000-20000mg/L, and the ammonia nitrogen content is 1000-5000 mg/L.
2. The process of claim 1 wherein the amount of weak oxidizing agent is controlled such that the sulfur compounds in the delayed coking sour water are thoroughly oxidized.
3. The method of claim 1, wherein the weak oxidant is at least one of air, iodine, iron oxide, and manganese dioxide.
4. The method of claim 3, wherein the weak oxidant is air.
5. The method of claim 1, wherein the alkylphenol aldehyde polyether has the formula H (C)2H4O)a(C3H6O)b(C2H4O)cO-(C6H4-CH2-)10Wherein (a + c)/b is 0.8-1。
6. The method of claim 5, wherein the alkylphenol aldehyde polyether has the formula H (C)2H4O)a(C3H6O)b(C2H4O)cO-(C6H4-CH2-)10Wherein (a + c)/b is 0.84 to 0.95.
7. The method of claim 1, wherein the alkylphenol aldehyde polyether is added in an amount of 5-200 ppm.
8. The method of claim 7, wherein the alkylphenol aldehyde polyether is added in an amount of 20-100 ppm.
9. The method of claim 1, wherein the conditions of the demulsification separation process comprise: the temperature is 10-60 ℃.
10. The method of claim 9, wherein the conditions of the demulsification separation process comprise: the temperature is 40-50 ℃.
11. The method of claim 9, wherein the conditions of the demulsification separation process further comprise: the time is 10min-6 h.
12. The method of claim 11, wherein the conditions of the demulsification separation process further comprise: the time is 50-90 min.
CN201710463172.6A 2017-06-19 2017-06-19 Method for purifying sulfur-containing sewage of delayed coking Active CN109133405B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710463172.6A CN109133405B (en) 2017-06-19 2017-06-19 Method for purifying sulfur-containing sewage of delayed coking

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710463172.6A CN109133405B (en) 2017-06-19 2017-06-19 Method for purifying sulfur-containing sewage of delayed coking

Publications (2)

Publication Number Publication Date
CN109133405A CN109133405A (en) 2019-01-04
CN109133405B true CN109133405B (en) 2021-10-08

Family

ID=64804108

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710463172.6A Active CN109133405B (en) 2017-06-19 2017-06-19 Method for purifying sulfur-containing sewage of delayed coking

Country Status (1)

Country Link
CN (1) CN109133405B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112062194B (en) * 2020-08-05 2023-04-18 国家能源集团煤焦化有限责任公司 Method for treating sulfur-containing sewage and bridge pipe

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102276127A (en) * 2010-06-10 2011-12-14 中国石油化工股份有限公司 Method for separating oily sludge and sands
CN102765767A (en) * 2012-07-12 2012-11-07 天津市瑞德赛恩新材料开发有限公司 Delay coking coke cooling water demulsifier composition and preparation method and application thereof
US20140057816A1 (en) * 2009-12-10 2014-02-27 Soane Energy, Llc Low interfacial tension surfactants for petroleum applications
WO2014166631A1 (en) * 2013-04-12 2014-10-16 Thyssenkrupp Industrial Solutions Ag Method for the improved cleaning of wastewater from a coke oven system
CN104496082A (en) * 2014-12-23 2015-04-08 马鞍山金泉工业介质科技有限公司 Separation treatment device for thermal treatment of wastewater and wastewater treatment method
CN106630296A (en) * 2017-01-04 2017-05-10 徐学文 Method for eliminating hydrogen sulfide and carbon monoxide in alkaline water of pipeline cleaning waste liquid of petrochemical oil refinery
CN106701156A (en) * 2017-01-06 2017-05-24 中国海洋石油总公司 Method for efficiently treating oil field complex oil-water emulsion
CN106745945A (en) * 2015-11-24 2017-05-31 中国石油天然气股份有限公司 A kind of oil-sand method for processing wash water

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5466483B2 (en) * 2009-10-15 2014-04-09 産協企業有限股▲ふん▼公司 Spherical activated carbon and manufacturing method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140057816A1 (en) * 2009-12-10 2014-02-27 Soane Energy, Llc Low interfacial tension surfactants for petroleum applications
CN102276127A (en) * 2010-06-10 2011-12-14 中国石油化工股份有限公司 Method for separating oily sludge and sands
CN102765767A (en) * 2012-07-12 2012-11-07 天津市瑞德赛恩新材料开发有限公司 Delay coking coke cooling water demulsifier composition and preparation method and application thereof
WO2014166631A1 (en) * 2013-04-12 2014-10-16 Thyssenkrupp Industrial Solutions Ag Method for the improved cleaning of wastewater from a coke oven system
CN104496082A (en) * 2014-12-23 2015-04-08 马鞍山金泉工业介质科技有限公司 Separation treatment device for thermal treatment of wastewater and wastewater treatment method
CN106745945A (en) * 2015-11-24 2017-05-31 中国石油天然气股份有限公司 A kind of oil-sand method for processing wash water
CN106630296A (en) * 2017-01-04 2017-05-10 徐学文 Method for eliminating hydrogen sulfide and carbon monoxide in alkaline water of pipeline cleaning waste liquid of petrochemical oil refinery
CN106701156A (en) * 2017-01-06 2017-05-24 中国海洋石油总公司 Method for efficiently treating oil field complex oil-water emulsion

Also Published As

Publication number Publication date
CN109133405A (en) 2019-01-04

Similar Documents

Publication Publication Date Title
RU2490309C2 (en) Method of diesel fuel denitration
AU763279B2 (en) Method of removing mercury in liquid hydrocarbon
KR20120020141A (en) Method of scavenging hydrogen sulfide from hydrocarbon stream
EP2465975A1 (en) Non-nitrogen sulfide sweeteners
US9267082B2 (en) Removal of mercury and mercuric compounds from crude oil streams
US4464251A (en) Removal of contaminants from organic compositions
JP2010248509A (en) Method for removing impurity from hydrocarbon oil
CN102079991A (en) Method for removing escapable sulfides from heavy hydrocarbons
CN109133405B (en) Method for purifying sulfur-containing sewage of delayed coking
Haruna et al. Comparative studies on reduction of sulphur content of heavy crude oil using KMnO4+ H2O2/CH3COOH and KMnO4+ H2O2/HCOOH via oxidative desulphurization (ODS)
CN111484872A (en) Residual oil demetalization method
JPS62250092A (en) Method for enhancing quality of diesel oil
US20100264065A1 (en) Membrane desulfurization of liquid hydrocarbon feedstreams
RU112188U1 (en) INSTALLATION OF SULFIDAL-ALKALINE DRAINAGE CLEANING
EP0509964B1 (en) Process for the treatment of spent aqueous solutions of caustic soda used for purification and washing of petroleum products
CA2245025C (en) Process for removing contaminants from thermally cracked waste oils
US3135680A (en) Process of refining diesel fuel with nitrogen dioxide
US11118118B2 (en) Process for reducing nitrogen content of hydrocarbon feed
CN113061481A (en) Recovery, purification and recycling process of waste mineral oil
US4752382A (en) Reducing the metals content of petroleum feedstocks
US11326109B2 (en) Metal removal from glycol fluids
RU2599782C1 (en) Recycling method for spent lubricants
Lazorko et al. Investigation of straight-run diesel oil fractions with sulphur high content oxidative desulphurization
CN115974643A (en) Enrichment and separation method of mercaptan sulfur-containing compounds in coking benzene hydrogenation xylene product
Ibrahim Desulphurisation of Petroleum Coke by Solvent Extraction

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant