CN102060350A - Deep treatment process of oily wastewater - Google Patents
Deep treatment process of oily wastewater Download PDFInfo
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Abstract
The invention relates to a deep treatment process of oily wastewater, which is characterized in that an absorption system and a regeneration system are provided in the process, wherein the absorption system is formed by a series of absorption tower groups with columns in series used for realizing parallel operation, the absorption tower groups are used for alternately performing deep treatment on oily yielding water with a low concentration of 30-50 mg/L of a traditional process, the absorption operation is carried out at normal temperature, the oil content in the yielding water is controlled to be lower than 1 mg/L through the treatment of a group of the absorption towers with columns in series, and an absorbing agent is made of modified fly ash, activated carbon and an expanded graphite absorbing material; when the yielding water in a group of the absorption towers exceeds a treatment requirement, the group of the absorption towers is switched to a biological regeneration system, and other absorption tower groups are simultaneously switched to the absorption system for continuous absorption; and saturated absorption towers are used for performing in-situ regeneration on the saturated absorbing agent by utilizing degradation ability of high temperature-resistant and efficient petroleum hydrocarbon for degrading bacteria.
Description
Technical field
The present invention relates to industry environmental protection and water-treatment technology field, be a kind of oily(waste)water advanced treatment process method, mainly be that the method that adopted the physical chemistry technology to combine with Measurement for Biochemistry realizes advanced treatment and the reuse to present oily(waste)water, thus the multiple effect that reaches environmental protection and save water and energy.
Background technology
Along with industry and expanding economy, human demand to the energy day by day increases, and has promoted the develop rapidly of petroleum industry; In oil production, storing, refining processing and use, have overflowing and discharging of petroleum hydrocarbon inevitably, cause the petroleum pollution of soil and water body.Some teratogenesis in the oil, carcinogenic substance also can be by food chain bioconcentration and direct harm humans health.
Therefore how the whole world has sizable zone still to be in the water resources shortage state, oily(waste)water is handled and reuse has crucial realistic meaning to control water environment pollution and conserve water resource.The wide material sources of oily(waste)water, at present seen correlation technique report are the treatment process for highly concentrated oil-bearing wastewater mostly, adopt " old three covers " treatment process more, and water outlet is difficult to reach the standard of discharging and reuse.Therefore at present the problem that exists of prior art is, can not effectively handle and causes pollution and waste to water resources oily(waste)water.
Summary of the invention
Purpose of the present invention and task provide the advanced treatment that a kind of effect stability, production run cost are low, the easy treatment process of operation operation is realized the lower concentration oily(waste)water, reach discharging and reuse standard.
The existence form of lower concentration oily(waste)water PetroChina Company Limited. hydrocarbon is based on dispersed oil and dissolving oil, and absorption method can effectively be handled the petroleum hydrocarbon particulate of particle diameter less than 10 μ m, and effluent quality is good, but makes its application be subjected to certain limitation because of problems such as the difficulties of regenerating.According to statistics, used gac can't reclaim, and the processing costs of waste water per ton will increase outside 0.8～0.9 yuan, and the saturated activity charcoal also can cause secondary pollution to environment.Therefore, the regeneration of sorbent material is significant.Hot method of reproduction (800～900 ℃) is to use at present the most sophisticated maximum, industrial renovation process, but only year treatment capacity greater than 500,000 tons big system economically feasible, and hot regeneration can cause the loading capacity loss of 5-15%.
For overcoming the deficiency that prior art exists, the present invention has done following design: the method that adopts the physical chemistry technology to combine with Measurement for Biochemistry realizes advanced treatment and the reuse to present oily(waste)water, promptly adopt absorption method that the lower concentration oily(waste)water is carried out advanced treatment, utilize the degradation capability of high temperature high efficiency petroleum hydrocarbon microorganism that saturated sorbent material is carried out in-situ regeneration, regeneration condition gentleness, stability height.Use oily(waste)water of the present invention just can reach discharging or reuse standard through primary treatment, can realize that waste water handles continuously, but saturated sorbent material adopts the in-situ regeneration mode to have operate continuously, it is low and avoid the advantage of numerous and diverse sorbent material cargo handling process to significantly reduce breakage, the regeneration cost of sorbent material, prolonged the work-ing life of sorbent material.
The present invention is a kind of oily(waste)water advanced treatment process method, it is characterized in that:
This technology is made of the absorption and two systems of regenerating:
Adsorption system is made of the placed in-line adsorption tower group of the multicolumn of a series of realization parallel runnings, alternately advanced treatment is carried out in lower concentration 30～50mg/L oil-containing water outlet of traditional technology, adsorption operations carries out at normal temperatures, be lower than 1mg/L through the one group of placed in-line adsorption tower processing controls of multicolumn water outlet oil-contg, sorbent material adopts modified coal ash, gac, expanded graphite sorbing material;
When the water outlet of this group adsorption tower surpasses processing requirements, this group is switched to bioregenerative system, meanwhile other adsorption tower groups are switched to adsorption system and carry out continuous adsorption; The saturated adsorption tower of this moment utilizes the degradation capability of high temperature high efficiency petroleum hydrocarbon degradation bacterium that saturated sorbent material is carried out in-situ regeneration;
When the water inlet oil-contg is 30～50mg/L, the absorption residence time is 5～60min, and the regeneration residence time is 1～48h, controls adsorption treatment water outlet oil-contg and is lower than 1mg/L, and the bio-regeneration number of times of saturated sorbent material reaches more than 40;
Described bioregenerative system, the composition of regenerated liquid comprise being the high-efficiency degradation bacterium series of the sole carbon source and energy growth with the petroleum hydrocarbon; Be selected from subtilis (Bacillus subtilis, CGMCC1.1377), Bacillus licheniformis (Bacillus licheniformis, CICC 10315), micrococcus luteus (Micrococcus luteus, CMCC28001), Pseudomonas aeruginosa (Pseudomonas, CICC10205) and pseudomonas putida (Pseudomonas, CICC 21906), the weight proportion of pressing 15-20%, 10-20%, 15-20%, 15-25%, 15-25% mixes; And can satisfy the necessary nitrogenous source of biological growth; Be selected from urea or ammonium sulfate, the phosphorus source; Be selected from dipotassium hydrogen phosphate or potassium primary phosphate; This fungus strain has the rich ability that produces the ability of thing tensio-active agent and tolerate 50-65 ℃ hot environment, to ensure the parsing for the adsorbent surface petroleum hydrocarbon;
When saturated adsorption tower group is carried out in-situ regeneration, the import and export of adsorption tower group link to each other with the regenerated liquid pipeline, the regenerated liquid temperature is 50-65 ℃, high temperature regeneration liquid carries out drip washing to saturated sorbent material, bio-surfactant and higher temperature promote the continuous parsing of absorption petroleum hydrocarbon in the lessivation, the petroleum hydrocarbon of resolving can constantly be broken the concentration gradient of petroleum hydrocarbon in solid phase surface and liquid phase, until finishing regenerative process by efficient degrading bacteria degraded, mineralising in the regeneration bacterium liquid.
According to the method described in the present invention, it is characterized in that:
This technology is made of the absorption and two systems of regenerating:
Sorbent material adopts modified coal ash, charcoal absorption material;
When the water inlet oil-contg is 40～50mg/L, the absorption residence time is 10～60min, and the regeneration residence time is 1.5～48h, controls adsorption treatment water outlet oil-contg and is lower than 1mg/L, and the bio-regeneration number of times of saturated sorbent material reaches more than 40;
Described bioregenerative system, the composition of regenerated liquid comprise being the high-efficiency degradation bacterium series of the sole carbon source and energy growth with the petroleum hydrocarbon; Be selected from subtilis (Bacillus subtilis, CGMCC1.1377), Bacillus licheniformis (Bacillus licheniformis, CICC 10315), micrococcus luteus (Micrococcus luteus, CMCC28001), Pseudomonas aeruginosa (Pseudomonas, CICC10205), press 18-20%, 15-20%, 18-20%, 18-25%, weight proportion mix; And can satisfy the necessary nitrogenous source of biological growth; Be selected from the urea ammonium, the phosphorus source; Be selected from dipotassium hydrogen phosphate.
The advanced treatment process method of above-mentioned oily(waste)water is applicable to the advanced treatment field of oil recovery and refinery water.
The present invention compared with prior art has following outstanding advantage and beneficial effect:
(1) solves the advanced treatment difficult problem of oily(waste)water, can realize the advanced treatment of lower concentration oily(waste)water, reach discharging and reuse standard.The method that this invention adopts the physical chemistry technology to combine with Measurement for Biochemistry realizes the advanced treatment to present oily(waste)water, promptly adopt absorption method that the lower concentration oily(waste)water is carried out advanced treatment, utilize the degradation capability of high temperature high efficiency petroleum hydrocarbon microorganism that saturated sorbent material is carried out in-situ regeneration, regeneration condition gentleness, stability are high, meet the theory of present low-carbon (LC).
(2) use oily(waste)water of the present invention just can reach discharging or reuse standard through primary treatment, can realize that waste water handles continuously, but saturated sorbent material adopts the in-situ regeneration mode to have operate continuously, it is low and avoid the advantage of numerous and diverse sorbent material cargo handling process to significantly reduce breakage, the regeneration cost of sorbent material, prolonged the work-ing life of sorbent material.Can realize continuous processing, application conditions gentleness, saving energy.
(3) earlier carry out the enrichment of petroleum hydrocarbon by adsorption treatment, be not subjected to the influence of factors such as oil-contg in the waste water, salt concn and pH, can be used for high salt, contain acid or contain the processing of extreme oily(waste)waters such as alkali, treatment effect is stable.
(4) have that one-time investment is low, the production run cost is low, the advantage that the operation operation is easy.
Embodiment
Embodiment 1
Secondary air-floatation water outlet with refinery is an example below, narrates specific implementation process of the present invention.
A kind of advanced treatment process of oily(waste)water, this technological process is described below:
The main water-quality guideline situation of the oily(waste)water of air supporting water outlet is as follows:
| Classification | CODcr | Volatile phenol | pH | Oil-contg |
| Content (mg/L) | 378.1-720.7 | 37.5-43.9 | 3.4 | 37.6-51.2 |
1) the air supporting water outlet goes out on advancing down through the placed in-line activated carbon adsorber of twin columns, and the absorption residence time is 15min, and control water outlet oil-contg＜1mg/L can processing waste water 429BV up to standard.After continuing absorption, the water outlet oil-contg is higher than 1mg/L, illustrates that reorganization adsorption tower adsorption site is occupied and need regenerate, and will reorganize adsorption tower and switch to regeneration system rapidly from adsorption system, and one group of placed in-line adsorption tower of twin columns that all the other are standby switches to adsorption system, the continuous processing of realization waste water.
2) will switch to the saturated adsorption tower group of regeneration system rapidly and regenerate, bio-regeneration liquid comprises resistant to elevated temperatures highly effective petroleum alkane degradation flora, and (the bacterium number reaches 1 * 10
8More than the CFU/ml, wherein the weight proportion of CGMCC1.1377, CICC 10315, CMCC28001, CICC 10205 and CICC 21906 is respectively 15%, 20%, 15%, 25%, 25%), urea 1.0g/L and dipotassium hydrogen phosphate 0.8g/L, potassium primary phosphate 0.2g/L, the regenerated liquid volume is 10: 1 with sorbent material volume ratio, the regenerated liquid temperature is 60 ℃, the regeneration residence time is 24h, and regeneration efficiency can reach 87.7%.
3) finish the adsorption tower group of bio-regeneration process, can continue to switch the attached system of resorption, carry out multiple adsorb-regeneration cycle of operation successively.Carry out 40 cycles of operation continuously, its bio-regeneration efficient can maintain about 75.1%, and this technology has stability preferably.
Embodiment 2
Advanced treatment with the oily(waste)water of oil recovery factory is an example, narrates specific implementation process of the present invention.
1) selecting the self-control modified coal ash for use is sorbent material, with flyash and modifier solution (V
Hydrochloric acid: V
Sulphur Acid=1: be that 1: 1 mixed is even with the buck mass volume ratio 3), carry out stirring reaction 3h under the ultrasonic wave effect, the oven dry back obtains modified fly ash absorbent.
2) oily(waste)water goes out on advancing down through the placed in-line modified coal ash adsorption tower of twin columns, and the absorption residence time is 10min, and the oil-contg of water inlet is (35.7-42.9mg/L), and control water outlet oil-contg＜1mg/L can processing waste water 217BV up to standard.After continuing absorption, the water outlet oil-contg is higher than 1mg/L, illustrates that reorganization adsorption tower adsorption site is occupied and need regenerate, and will reorganize adsorption tower and switch to regeneration system rapidly from adsorption system, and one group of placed in-line adsorption tower of twin columns that all the other are standby switches to adsorption system, the continuous processing of realization waste water.
3) will switch to the saturated adsorption tower group of regeneration system rapidly regenerates, bio-regeneration liquid comprises resistant to elevated temperatures highly effective petroleum alkane degradation flora (with embodiment 1), and the regenerated liquid volume is 15: 1 with sorbent material volume ratio, and the regenerated liquid temperature is 60 ℃, the regeneration residence time is 24h, and regeneration efficiency can reach 78%.
4) finish the adsorption tower group of bio-regeneration process, can continue to switch the attached system of resorption, carry out multiple adsorb-regeneration cycle of operation successively.Carry out 40 cycles of operation continuously, its bio-regeneration efficient can maintain about 75%, and this technology has stability preferably.
Embodiment 3
Secondary air-floatation water outlet with refinery is an example below, narrates specific implementation process of the present invention.
A kind of advanced treatment process of oily(waste)water, this technological process is described below:
The main water-quality guideline situation of the oily(waste)water of air supporting water outlet is as follows:
| Classification | CODcr | Volatile phenol | pH | Oil-contg |
| Content (mg/L) | 378.1-720.7 | 37.5-43.9 | 3.4 | 37.6-51.2 |
1) with 900 ℃ down expanded make expanded graphite with greater than the rubber powder granule of 20 order particle diameters mixed according to 8:1, adopt dry column-packing, 3cm thick fiberglass on the adsorption tower upper and lower end pad.
2) the air supporting water outlet goes out on advancing down through the placed in-line expanded graphite of twin columns-rubber powder adsorption tower, and the absorption residence time is 30min, and control water outlet oil-contg＜1mg/L can processing waste water 321BV up to standard.After continuing absorption, the water outlet oil-contg is higher than 1mg/L, illustrates that reorganization adsorption tower adsorption site is occupied and need regenerate, and will reorganize adsorption tower and switch to regeneration system rapidly from adsorption system, and one group of placed in-line adsorption tower of twin columns that all the other are standby switches to adsorption system, the continuous processing of realization waste water.
3) will switch to the saturated adsorption tower group of regeneration system rapidly regenerates, bio-regeneration liquid comprises resistant to elevated temperatures highly effective petroleum alkane degradation flora (with embodiment 1), and the regenerated liquid volume is 20: 1 with sorbent material volume ratio, and the regenerated liquid temperature is 55 ℃, the regeneration residence time is 48h, and regeneration efficiency can reach 82%.
4) finish the adsorption tower group of bio-regeneration process, can continue to switch the attached system of resorption, carry out multiple adsorb-regeneration cycle of operation successively.Carry out 45 cycles of operation continuously, its bio-regeneration efficient can maintain about 70%, and this technology has stability preferably.
Claims (2)
1. oily(waste)water advanced treatment process method is characterized in that:
This technology is made of the absorption and two systems of regenerating:
Adsorption system is made of the placed in-line adsorption tower group of the multicolumn of a series of realization parallel runnings, alternately advanced treatment is carried out in lower concentration 30～50mg/L oil-containing water outlet of traditional technology, adsorption operations carries out at normal temperatures, be lower than 1mg/L through the one group of placed in-line adsorption tower processing controls of multicolumn water outlet oil-contg, sorbent material adopts modified coal ash, gac, expanded graphite sorbing material;
When the water outlet of this group adsorption tower surpasses processing requirements, this group is switched to bioregenerative system, meanwhile other adsorption tower groups are switched to adsorption system and carry out continuous adsorption; The saturated adsorption tower of this moment utilizes the degradation capability of high temperature high efficiency petroleum hydrocarbon degradation bacterium that saturated sorbent material is carried out in-situ regeneration;
When the water inlet oil-contg is 30～50mg/L, the absorption residence time is 5～60min, and the regeneration residence time is 1～48h, controls adsorption treatment water outlet oil-contg and is lower than 1mg/L, and the bio-regeneration number of times of saturated sorbent material reaches more than 40;
Described bioregenerative system, the composition of regenerated liquid comprise being the high-efficiency degradation bacterium series of the sole carbon source and energy growth with the petroleum hydrocarbon; Be selected from subtilis Bacillus subtilis, CGMCC 1.1377, Bacillus licheniformis Bacillus licheniformis, CICC 10315, micrococcus luteus Micrococcus luteus, CMCC28001, Pseudomonas aeruginosa Pseudomonas, CICC 10205 and pseudomonas putida Pseudomonas, CICC21906, the weight proportion of pressing 15-20%, 10-20%, 15-20%, 15-25%, 15-25% mixes; And can satisfy the necessary nitrogenous source of biological growth; Be selected from urea or ammonium sulfate, the phosphorus source; Be selected from dipotassium hydrogen phosphate or potassium primary phosphate; This fungus strain has the rich ability that produces the ability of thing tensio-active agent and tolerate 50-65 ℃ hot environment, to ensure the parsing for the adsorbent surface petroleum hydrocarbon;
When saturated adsorption tower group is carried out in-situ regeneration, the import and export of adsorption tower group link to each other with the regenerated liquid pipeline, the regenerated liquid temperature is 50-65 ℃, high temperature regeneration liquid carries out drip washing to saturated sorbent material, bio-surfactant and higher temperature promote the continuous parsing of absorption petroleum hydrocarbon in the lessivation, the petroleum hydrocarbon of resolving can constantly be broken the concentration gradient of petroleum hydrocarbon in solid phase surface and liquid phase, until finishing regenerative process by efficient degrading bacteria degraded, mineralising in the regeneration bacterium liquid.
2. it is characterized in that in accordance with the method for claim 1:
This technology is made of the absorption and two systems of regenerating:
Sorbent material adopts modified coal ash, charcoal absorption material;
When the water inlet oil-contg is 40～50mg/L, the absorption residence time is 10～60min, and the regeneration residence time is 1.5～48h, controls adsorption treatment water outlet oil-contg and is lower than 1mg/L, and the bio-regeneration number of times of saturated sorbent material reaches more than 40;
Described bioregenerative system, the composition of regenerated liquid comprise being the high-efficiency degradation bacterium series of the sole carbon source and energy growth with the petroleum hydrocarbon; Be selected from subtilis Bacillus subtilis, CGMCC 1.1377, Bacillus licheniformis Bacillus licheniformis, CICC 10315, micrococcus luteus Micrococcus luteus, CMCC28001, Pseudomonas aeruginosa Pseudomonas, CICC 10205, press 18-20%, 15-20%, 18-20%, 18-25%, weight proportion mix; And can satisfy the necessary nitrogenous source of biological growth; Be selected from the urea ammonium, the phosphorus source; Be selected from dipotassium hydrogen phosphate.
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