CN108101262B - Gas water purification method - Google Patents
Gas water purification method Download PDFInfo
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- CN108101262B CN108101262B CN201711409147.6A CN201711409147A CN108101262B CN 108101262 B CN108101262 B CN 108101262B CN 201711409147 A CN201711409147 A CN 201711409147A CN 108101262 B CN108101262 B CN 108101262B
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- polyoxyethylene ether
- gas water
- fatty amine
- amine polyoxyethylene
- recovery
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- 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
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- 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
- C02F2001/007—Processes including a sedimentation step
Abstract
The invention discloses a gas water purification method, which comprises the following steps: after adding fatty amine polyoxyethylene ether into the gas water recovery circulation system, cooling; carrying out sedimentation separation on the gas water cooled in the step 1) through a gas water separation device, and removing sediment and oil liquid to obtain residual liquid; introducing the residual liquid obtained in the step 2) into a phenol ammonia recovery system for recovery treatment, and finishing purification; in the step 1), the EO number of the fatty amine polyoxyethylene ether is 6-15, the carbon chain length is 12-22, and in the purification method, through selection of specific fatty amine polyoxyethylene ether, effective separation of oil in gas water can be realized by only adding one chemical component in a gas water recycling circulation system, so that the purification cost is reduced, and the purification process is simplified.
Description
Technical Field
The invention relates to the technical field of coal chemical production, in particular to a method for purifying gas water.
Background
In the modern rapid development age, both in China and in the world, the energy consumption demand is increasing day by day, and the coal-rich, oil-poor and gas-poor coal-rich chemical industry is the basic structure of energy in China, so that the development of the coal-rich chemical industry taking coal as the raw material is a necessary choice in China.
The coal chemical industry refers to a process of converting coal into gas, liquid and solid fuels and chemicals by using the coal as a raw material through chemical processing, and mainly comprises gasification, liquefaction, dry distillation, tar processing, calcium carbide acetylene chemical industry and the like of the coal. Among the production technologies available in the coal industry, coking is the earliest process used and still remains an important component of the chemical industry to date. Coal gasification plays an important role in coal chemical industry, is used for producing various gas fuels and is clean energy, and synthesis gas produced by coal gasification is a raw material for synthesizing various products such as liquid fuels, chemical products and the like.
The coal gas water produced in the production process of the coal chemical industry needs to be treated, the coal gas water contains a large amount of oil, dust, suspended matters, phenol, ammonia and other substances, the oil-containing phenol water is subjected to reduced pressure flash evaporation after being separated by a coal gas water separation device, oil, phenol water and dust are separated, part of emulsified oil, dissolved oil and dust can not be effectively separated and enter a post-system phenol-ammonia recovery device, and thus a heat exchanger and a tower tray are blocked, so that dehydrosulfuration, deamination and extraction are influenced, high-load long-period operation of the device is not facilitated, energy consumption is greatly increased, the production capacity of equipment is reduced, the maintenance cost of a tower cleaning is increased, the production cost investment is increased, the phenol-ammonia recovery device can not normally operate, the biochemical treatment device can not normally operate, the wastewater can not reach the standard, zero discharge of the wastewater can not be realized, and the problem is always. In order to realize zero discharge of wastewater, the residual wastewater generated in the production process needs to be further treated, but the wastewater treatment difficulty is very high, the zero discharge of the wastewater in the coal chemical industry is hardly realized in the real sense, and the coal chemical industry enterprises are very easy to cause pollution to the environment. The method is also a bottleneck problem in the development of the coal chemical industry, so that the realization of zero discharge of wastewater is the most critical problem restricting the development of the coal chemical industry, and is also the environmental protection policy red line required by enterprises in the coal chemical industry in China at present.
Although methods for purifying gas water have been developed before, many kinds of chemicals need to be added, which results in high cost and complex operation of enterprises in the process of purifying gas water, and therefore, how to develop a simple process or method for purifying gas water becomes a problem to be solved urgently.
Disclosure of Invention
In view of this, the present invention discloses a gas water purification method, which at least solves the problems of high purification cost, complex operation, etc. existing in the prior gas water purification method.
The technical scheme provided by the invention specifically is a gas water purification method, which comprises the following steps:
1) after adding fatty amine polyoxyethylene ether into the gas water recovery circulation system, cooling;
2) carrying out sedimentation separation on the gas water cooled in the step 1) through a gas water separation device, and removing sediment and oil liquid to obtain residual liquid;
3) introducing the residual liquid obtained in the step 2) into a phenol ammonia recovery system for recovery treatment, and finishing purification;
wherein the EO number of the fatty amine polyoxyethylene ether in the step 1) is 6-15, and the carbon chain length is 12-22.
Preferably, the fatty amine polyoxyethylene ether is a double-bond-containing fatty amine polyoxyethylene ether.
More preferably, the fatty amine polyoxyethylene ether is oleylamine polyoxyethylene ether.
Further preferably, the fatty amine polyoxyethylene ether in the step 1) is added at a circulating water pumping inlet of a gas water recovery circulating system.
More preferably, the addition amount of the fatty amine polyoxyethylene ether accounts for 100ppm to 300ppm of the yield of the coal tar in the recovery circulation system, or the addition amount of the fatty amine polyoxyethylene ether accounts for 10ppm to 30ppm of the water amount of the phenol water generated in the recovery circulation system.
Further preferably, the addition mode of the fatty amine polyoxyethylene ether is continuous addition.
According to the method for purifying the coal gas water, the fatty amine polyoxyethylene ether with the EO number of 6-15 and the carbon chain length of 12-22 is added into the coal gas water recovery circulation system to realize oil liquid stratification in the coal gas water, the sediments and the oil liquid in the coal gas water are separated through the coal gas water separation device, and finally phenol and ammonia substances in the coal gas water are extracted through the phenol-ammonia recovery system, so that the purification of the coal gas water is realized, the problems of blockage, stop and the like in the coal gas water recovery circulation system are prevented, the service life and the maintenance period of the recovery circulation system are greatly prolonged, the maintenance cost is reduced, and the zero emission of the coal gas water is realized. In the purification method, through the selection of specific fatty amine polyoxyethylene ether, the effective separation of oil in gas water can be realized by only adding one chemical component in a gas water recovery circulation system, the purification cost is reduced, and the purification process is simplified.
Detailed Description
Exemplary embodiments will be described in detail herein. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. Rather, they are merely examples of methods consistent with certain aspects of the invention, as detailed in the appended claims.
The embodiment provides a gas water purification method, which comprises the following specific steps:
1) after adding fatty amine polyoxyethylene ether into the gas water recovery circulation system, cooling;
2) carrying out sedimentation separation on the gas water cooled in the step 1) through a gas water separation device, and removing sediment and oil liquid to obtain residual liquid;
3) introducing the residual liquid obtained in the step 2) into a phenol ammonia recovery system for recovery treatment, and finishing purification;
wherein the EO number of the fatty amine polyoxyethylene ether in the step 1) is 6-15, and the carbon chain length is 12-22.
The fatty amine polyoxyethylene ether has functional groups required by both oleophylicity and hydrophilcity, is a very good surfactant, and can stratify emulsified oil, soluble oil, sediments and water in gas water. The fatty amine polyoxyethylene ether is obtained by addition reaction of higher fatty amine and ethylene oxide, shows certain property of a cationic surfactant when the number of polyoxyethylene groups is small, gradually weakens the cationic property along with the growth of polyoxyethylene chains, shows the property of a nonionic surfactant, has two polyoxyethylene ether chains, one nitrogen atom and one long-chain fatty group in a molecule, has multiple functions of washing, level dyeing, permeation, staining resistance, dispersion and the like, and is widely applied to the fields of textile, printing and dyeing, food, medicine, cosmetics and the like. The double bond in the aliphatic amine has unsaturation, so that the lipophilic group has better activity and better effect. The high carbon chain double bond fatty amine has good cold water washing performance and good dirt removing capability. The molecular structure contains an amine structure, and when the EO number is lower, the alkali resistance is poor, and the compatibility with an anionic surfactant is poor. As the EO number increases, alkali resistance increases, and compatibility with an anionic surfactant increases. Also has the characteristics of anti-redeposition of dirt, rust prevention, no gel, low solidifying point and the like.
The experiment shows that: 6-15 EO fatty amine polyoxyethylene ether, namely 6-15 EO ethylene oxide containing oil has particularly outstanding oil-water separation effect in coal gas water. If the EO number of the adopted fatty amine polyoxyethylene ether is lower than 6, excessive lipophilicity can occur, so that the problem that light tar is recycled into heavy tar is too much, and the yield of the light tar is reduced; if the EO number of the aliphatic amine oxyethylene ether is higher than 15, excessive hydrophilicity will appear, resulting in too high water content of the tar and reduced quality of the tar. From the product structure, the low carbon chain product with the carbon chain length less than 12 has poor cleaning effect and permeability, and cannot realize good purification effect, while the product with the carbon chain length more than 22 has good lubricating effect, but is not suitable for the field of coal chemical industry.
Preferably, the fatty amine polyoxyethylene ether is fatty amine polyoxyethylene ether containing double bonds, and the double bonds in the oleylamine enable the lipophilic groups to have better activity, so that the effect is better. The advantages of the double bond: the double bond is a multiple bond formed by two pairs of common electrons between two atoms in a compound molecule. If two atoms form a sigma bond and then each have an unpaired p electron, they may overlap to form a pi bond, the combination (sigma + pi) being called a double bond, usually represented by the two dashes a ═ B, e.g. H2C＝CH2(ethylene). The carbon atom and the carbon atom C ═ C are combined by a double bond, the organic compound containing the double bond has unsaturation, can perform addition reaction and polymerization reaction, and improves the purification effect, and more preferably, the fatty amine polyoxyethylene ether is oleylamine polyoxyethylene ether.
Wherein the fatty amine polyoxyethylene ether in the step 1) is added at a circulating water pumping inlet of a gas water recovery circulating system, and the addition amount of the fatty amine polyoxyethylene ether accounts for 100ppm to 300ppm of the yield of the coal tar in the recovery circulating system, or the addition amount of the fatty amine polyoxyethylene ether accounts for 10ppm to 30ppm of the amount of the phenol water generated in the recovery circulating system. Preferably, the addition mode of the fatty amine polyoxyethylene ether is continuous addition.
The present invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention.
The method for purifying the gas water carries out actual purification and oil removal experiments in a certain gasification branch factory from 6 months 1 days in 2017 to 10 months 15 days in 2017, and comprises the following specific processes: continuously adding 200ppm of fatty amine polyoxyethylene ether accounting for the yield of coal tar in a recovery circulation system at a circulating water pump suction inlet of the coal gas water recovery circulation system, cooling, performing sedimentation separation on the cooled coal gas water by a coal gas water separation device, removing sediments and oil liquid to obtain residual liquid, introducing the residual liquid into a phenol ammonia recovery system for recovery treatment, and finishing purification. Wherein, in the experimentation, in order to ensure the accuracy of experimental data, adopt to add the form that medicine was stopped for half a month to gas water recovery circulation system to the medicine that adds before preventing produces the influence to follow-up medicine that adds, specific medicine circumstances is: adding fatty amine polyoxyethylene ether with EO number of 15 and carbon chain length of 22 from 6 months 1 days in 2017 to 6 months 15 days in 2017; adding fatty amine polyoxyethylene ether with EO number of 6 and carbon chain length of 12 from 30 days in 6 months in 2017 to 16 days in 7 months in 2017; adding fatty amine polyoxyethylene ether with EO number of 8 and carbon chain length of 14 into the mixture from 30 months in 2017 to 15 months in 8 months in 2017; adding fatty amine polyoxyethylene ether with EO number of 5 and carbon chain length of 12 from 30 months in 2017 to 15 months in 2017; adding fatty amine polyoxyethylene ether with EO number of 16 and carbon chain length of 23 into the mixture from 30/2017/9 to 15/2017/10/15, and then respectively sampling and inspecting the sewage generated in coal chemical production, the purified sewage (sewage at an inlet for recycling phenol and ammonia) and the sewage at an outlet for recycling phenol and ammonia in the steps of 6/15/2017, 7/16/2017, 8/15/2017, 9/15/2017 and 15/2017/10/15, wherein specific inspection results refer to examples 1 to 5.
Example 1
The following test results are obtained using the fatty amine polyoxyethylene ether 15EO carbon chain C22
Remarking: high oil removing rate, high tar water content higher than 4, and good fluidity of the suspended matters reduced tar.
Example 2
The following test results are obtained using fatty amine polyoxyethylene ether 6EO carbon chain C12
Remarking: high oil removal rate, low tar water content below 4, light tar returning to tar and low tar specific weight.
Example 3
The following test results are obtained using fatty amine polyoxyethylene ether 8EO carbon chain C14
Remarking: high oil removing rate, low water content of tar (less than 5), and good fluidity of tar reduced by suspended matters.
Example 4
The following test results are obtained using fatty amine polyoxyethylene ether EO5 carbon chain C12
Remarking: the oil removal rate is low, the water content of tar is lower than 2, light tar returns to the tar, the specific gravity of the tar is reduced, suspended matters are not reduced, and the oil mobility is poor.
Example 5
The following test results are obtained using fatty amine polyoxyethylene ether EO16 carbon chain C23
Remarking: the oil removal rate is low, the water content of tar is higher than 5, and the reduction of suspended matters is not obvious.
Wherein, the experiment shows that: the purification effect of the oleylamine polyoxyethylene ether with double bonds is superior to that of other fatty amine polyoxyethylene ethers.
Comparative example 1
During the period from 10 months and 30 days in 2017 to 11 months and 15 days in 2017, the gas water purification method is used for carrying out another purification and oil removal experiment in the same gasification branch factory as the gasification branch factory in the embodiment 1-5, and the specific process is as follows: continuously adding a purification auxiliary agent which accounts for 200ppm of the yield of coal tar in a recovery circulation system at a circulating water pump suction inlet of the coal gas water recovery circulation system, cooling, carrying out sedimentation separation on the cooled coal gas water by a coal gas water separation device, removing sediments and oil liquid to obtain residual liquid, introducing the residual liquid into a phenol ammonia recovery system for recovery treatment, and finishing purification, wherein the purification auxiliary agent consists of 99 parts of oleylamine polyoxyethylene ether and 1 part of fatty amine, the EO number of the oleylamine polyoxyethylene ether is 19, and the length of a carbon chain is 8. Sampling and inspecting the sewage generated in coal chemical production, the purified sewage (the sewage at the phenol-ammonia recovery inlet) and the sewage at the phenol-ammonia recovery outlet respectively in 2017, 11 months and 15 days, wherein specific inspection results are shown in the following table.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It will be understood that the invention is not limited to the above description but is capable of numerous modifications and variations without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (3)
1. A gas water purification method is characterized by comprising the following steps:
1) after adding fatty amine polyoxyethylene ether into the gas water recovery circulation system, cooling;
2) carrying out sedimentation separation on the gas water cooled in the step 1) through a gas water separation device, and removing sediment and oil liquid to obtain residual liquid;
3) introducing the residual liquid obtained in the step 2) into a phenol ammonia recovery system for recovery treatment, and finishing purification;
wherein the EO number of the fatty amine polyoxyethylene ether in the step 1) is 6-15, and the carbon chain length is 12-22;
the fatty amine polyoxyethylene ether is fatty amine polyoxyethylene ether containing double bonds;
the addition amount of the fatty amine polyoxyethylene ether accounts for 100-300 ppm of the yield of the coal tar in the recovery circulation system, or the addition amount of the fatty amine polyoxyethylene ether accounts for 10-30 ppm of the water amount of the phenol water generated in the recovery circulation system;
the fatty amine polyoxyethylene ether is oleylamine polyoxyethylene ether.
2. The gas water purification method according to claim 1, wherein the fatty amine polyoxyethylene ether in the step 1) is added at a circulating water pumping inlet of a gas water recovery circulation system.
3. The gas water purification method according to claim 1, wherein the fatty amine polyoxyethylene ether is added continuously.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102839007A (en) * | 2011-06-24 | 2012-12-26 | 上海宝钢化工有限公司 | Demulsification, neutralization and dehydration method of acidic emulsified tar |
| CN105236680A (en) * | 2015-10-13 | 2016-01-13 | 张征北 | Method for purifying gas liquor |
| CN105668846A (en) * | 2016-01-15 | 2016-06-15 | 中国石油大学(华东) | Fine processing technology of coal chemical aromatics-containing wastewater |
| CN106630090A (en) * | 2017-03-21 | 2017-05-10 | 张征北 | Purification method of wastewater in coal chemical industry |
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- 2017-12-22 CN CN201711409147.6A patent/CN108101262B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102839007A (en) * | 2011-06-24 | 2012-12-26 | 上海宝钢化工有限公司 | Demulsification, neutralization and dehydration method of acidic emulsified tar |
| CN105236680A (en) * | 2015-10-13 | 2016-01-13 | 张征北 | Method for purifying gas liquor |
| CN105668846A (en) * | 2016-01-15 | 2016-06-15 | 中国石油大学(华东) | Fine processing technology of coal chemical aromatics-containing wastewater |
| CN106630090A (en) * | 2017-03-21 | 2017-05-10 | 张征北 | Purification method of wastewater in coal chemical industry |
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