CN103663826B - A kind of pretreatment process of HTS factory effluent - Google Patents
A kind of pretreatment process of HTS factory effluent Download PDFInfo
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- CN103663826B CN103663826B CN201210350718.4A CN201210350718A CN103663826B CN 103663826 B CN103663826 B CN 103663826B CN 201210350718 A CN201210350718 A CN 201210350718A CN 103663826 B CN103663826 B CN 103663826B
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Abstract
The present invention relates to a kind of pretreatment process of HTS factory effluent, the method comprises: the pH value of described HTS factory effluent be adjusted to and be greater than 11, distilled the waste water obtained after adjust ph.Adopt described method of the present invention to carry out pre-treatment to HTS factory effluent, make to obtain significant raising through the B/C of pretreated waste water, thus significantly improve the biodegradability of HTS factory effluent.
Description
Technical field
The present invention relates to a kind of pretreatment process of HTS factory effluent.
Background technology
The synthesis of HTS and the successful Application as organism catalyst for selective oxidation, be considered to a milestone in molecular sieve catalytic eighties field.At present, the principal reaction adopting HTS to carry out organic compound selective oxidation has the oxidising process of the organic compound such as oxidation of alkene epoxidation, arene hydroxylation, ketone ammonia oxidation, oxidation of alkanes and alcohol.Catalyst system with other type is compared, and employing HTS has reaction conditions gentleness as the system that catalyzer carries out being oxidized, oxidation object product yield is high, selectivity good and the simple remarkable advantage of technological process; And owing to using lower concentration hydrogen peroxide oxidant, oxidation source is easy to get safely, and reduzate is water, does not introduce impurity to reaction system.
Research Institute of Petro-Chemical Engineering adopts the titanium-silicon molecular sieve catalyst of the new technology synthesis such as low temperature plastic, high temperature crystallization and rearrangement modification to improve the oxidizing reaction performance of molecular sieve, solves HTS synthesis and is difficult to the not easily stable problem of repetition, reactive behavior.Hunan Jianchang Petrochemical Co., Ltd adopts this technology to build up the HTS manufacture gasifying device of 200 tons/year, and this molecular sieve catalyst obtains application in the techniques such as cyclohexanone oxamidinating, has good economic benefit.But it is high that the waste water produced in the production process of HTS has organic content, the features such as biodegradability difference.Kill or the material of inhibition containing having microorganism in waste water, direct discharging of waste water can bring great impact to existing biochemical treatment apparatus.
At present, in existing document, the report of the treatment process of molecular sieve catalytic agent production waste water is focused mostly in oil refining molecular sieve catalyst.Such as, " biological treatment of catalyst production process ammonia-containing water " (Industrial Catalysis the 16th volume o. 11th in 2008, Gao Huijie, Li Yuansheng etc.) nitrifier of middle cultivation processes the ammonia-containing water that catalyst production process is discharged, after continuous reaction apparatus adds thalline, hydraulic detention time is 17.5h, and water outlet ammonia nitrogen can lower than 10mgL
-1, ammonia nitrogen removal frank is 95%.Result shows, the bacterial classification of preservation is activity recovery after adaptation in 2-7 days, can by ammonia nitrogen concentration lower than 1500mgL
-1catalyst production waste water deamination to being less than 10mgL
-1.But these treatment processs focus on removing ammonia nitrogen in waste water, and in the factory effluent of oil refining molecular sieve catalyst, chemical oxygen demand (COD) (COD) is not high, and good biodegradability, can directly process by the method for biochemical treatment.And the COD of HTS factory effluent is higher, biodegradability is poor, can not directly adopt the method for biochemical treatment to process, and therefore, the treatment process of existing molecular sieve catalytic agent production waste water not being suitable for processes HTS factory effluent.
Summary of the invention
The object of the invention is the treatment process in order to overcome existing molecular sieve catalytic agent production waste water and be not suitable for the defect that HTS factory effluent is processed, a kind of pretreatment process of HTS factory effluent is provided.
The invention provides a kind of pretreatment process of HTS factory effluent, the method comprises: the pH value of described HTS factory effluent be adjusted to and be greater than 11, distilled the waste water obtained after adjust ph.
The pretreatment process of HTS factory effluent according to the present invention, by HTS factory effluent being carried out distill the chemical oxygen demand (COD) (COD) that significantly can reduce the waste water steamed, and significantly improve the ratio (B/C) of biochemical oxygen demand (BOD) (BOD) and chemical oxygen demand (COD) (COD), thus improve the biodegradability of the waste water that this steams, the waste water steamed can be entered in follow-up biochemical treatment system and carry out biochemical treatment.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The pretreatment process of HTS factory effluent according to the present invention comprises: the pH value of described HTS factory effluent be adjusted to and be greater than 11, distilled the waste water obtained after adjust ph.
In the present invention, described HTS factory effluent can for the waste water produced in conventional HTS production process.Usually, the organic content in described HTS factory effluent is higher, and make its COD higher, be generally greater than 20000mg/L, such as 21000-40000mg/L, B/C are less than 0.1, such as 0.01-0.08, and biodegradability is poor.Thus, biochemical processing method directly cannot process described HTS factory effluent.In addition, consider that biochemical processing method is the method for advantage of lower cost in numerous method of wastewater treatment.For this reason, the present inventor attempts to carry out pre-treatment to improve its biodegradability to HTS factory effluent.After many trials, the present inventor is surprised to find that, by distilling HTS factory effluent, the biodegradability of the waste water steamed can be significantly improved, the waste water steamed can be entered in follow-up biochemical treatment system and carry out biochemical treatment, thus complete the present invention.
In the present invention, the pH value of described HTS factory effluent is generally less than 11, such as 9-11.If the pH value of described HTS factory effluent was not adjusted to and is greater than 11 before enforcement distillation, then, after the lower and described still-process of the B/C of distillate carries out for some time, can jelly be separated out, cover on still kettle wall and affect distilling effect; And in this case, can only steam the waste water of 75 below volume %, make the debris that obtains after distillation still more, intractability is larger.
In described method of the present invention, in order to as much as possible described HTS factory effluent be distilled, and ensure that the waste water steamed meets the requirement of biochemical treatment, preferably the pH value of described HTS factory effluent is adjusted to more than 12, is preferably adjusted to 12-13 further.Here, the reagent of adjust ph can be sodium carbonate and/or sodium hydroxide.
In described method of the present invention, described in the volume of waste water that steams for the 80-99% of the volume of waste water obtained after described adjust ph, 90-97% can be preferably.
For the described waste water steamed, its B/C is higher, is generally more than 0.15, is preferably more than 0.3, is more preferably 0.35-0.65.The described waste water steamed directly can carry out biochemical treatment separately, carries out biochemical treatment after also can mixing with other waste water.Other waste water described can be the waste water that can carry out biochemical treatment, as oil refining molecular sieve catalytic agent production waste water, also can be the waste water that can not carry out biochemical treatment, as HTS factory effluent.When carrying out biochemical treatment after being mixed with the waste water that can not carry out biochemical treatment by the described waste water steamed, need to ensure that COD and B/C of mixed waste water meets the requirement of biochemical processing method.The method of described biochemical treatment can be the conventional biochemical processing method used in field of waste water treatment, such as activated sludge process, biological contact oxidation process, Gas biological filter, sequencing batch reactor, anaerobic biofilter method, anaerobic contact method, anaerobic-anoxic-oxic method or anoxic-anaerobic-aerobic process.
In the preferred case, in order to the biochemical treatment efficiency of waste water steamed described in improving, before the described waste water steamed is carried out biochemical treatment, the pH value of the described waste water steamed is adjusted to 6-9, is more preferably 7-8.Here, the reagent of adjust ph can be at least one in hydrochloric acid, sulfuric acid and nitric acid.
For the debris obtained after distillation, its COD is higher, usually between 80,000 mg/L to 70 ten thousand mg/L, has obvious pungent smell.The present inventor is surprised to find that, when the pH value of described debris being adjusted to below 8, this debris can become g., jelly-like material, and does not have obvious smell.Therefore, in the preferred case, the pH value of described debris is adjusted to less than 8, is more preferably 5-8.Here, the reagent of adjust ph can be at least one in hydrochloric acid, sulfuric acid and nitric acid.For the g., jelly-like material obtained after reconciling pH value, because COD is higher, and small volume, therefore, can process by non-biochemical processing method conveniently, such as, at least one mode in burning disposal, supercritical oxidation process and landfill disposal can be adopted to process described g., jelly-like material.Described burning disposal, supercritical oxidation process and landfill disposal are the conventional practice of refuse process field, do not repeat them here.
The invention will be further described with comparative example by the following examples.
The HTS factory effluent used in following examples and comparative example is as shown in table 1 below.
Table 1
| Project | Wastewater sample 1 | Wastewater sample 2 |
| PH value | 10.8 | 10.7 |
| COD（mg/L） | 32150 | 24020 |
| BOD（mg/L） | 1000 | 1500 |
| B/C | 0.03 | 0.06 |
| Specific conductivity (μ S/cm) | 3960 | 4280 |
Embodiment 1
The present embodiment is for illustration of the pretreatment process of described HTS factory effluent of the present invention.
Get the wastewater sample 1 shown in 600ml table 1, with sodium hydroxide, pH value is adjusted to 12.3, water sample is placed in the single port flask of 1000ml.Single port flask is placed on electric heating cover, and the outlet of single port flask is connected to snake type prolong, and the prolong the other end is connected to Erlenmeyer flask with a scale.Connect the water coolant of prolong, open electric heating cover and waste water is distilled.After steaming the waste water sample of 570ml, stop distillation.The pH value of the waste water steamed is 10.6, COD be 3500mg/L, B/C is 0.53.
Comparative example 1
Processed by the wastewater sample 1 shown in Fenton oxidation method his-and-hers watches 1, the condition of process comprises: pH value is 5, and the dosage of hydrogen peroxide is 6000ppm, and the dosage of ferrous sulfate is 12000ppm, and the reaction times is 2 hours.Learn by measuring, the COD of the reuse water obtained after process is 29970mg/L, BOD be 1199mg/L, B/C is 0.04.
Comparative example 2
Processed by the wastewater sample 1 shown in wet oxidation process his-and-hers watches 1, the condition of process comprises: temperature of reaction is 220 DEG C, reaction pressure 3.5MPa, and the reaction times is 4 hours.Learn by measuring, the COD of the reuse water obtained after process is 30180mg/L, BOD be 1509mg/L, B/C is 0.05.
Comparative example 3
Wastewater sample 1 according to the method his-and-hers watches 1 of embodiment 1 carries out pre-treatment, and difference is, does not regulate the pH value of this wastewater sample, and, in still-process, when the volume of the waste water steamed is 450ml, adularescent Precipitation in single port flask, thus stops distillation.The pH value of the waste water steamed is 8, COD be 56807mg/L, B/C is 0.12.
Embodiment 3
The present embodiment is for illustration of the pretreatment process of described HTS factory effluent of the present invention.
Get the wastewater sample 1 shown in 600ml table 1, with sodium hydroxide, pH value is adjusted to 13, water sample is placed in the single port flask of 1000ml.Single port flask is placed on electric heating cover, and the outlet of single port flask is connected to snake type prolong, and the prolong the other end is connected to Erlenmeyer flask with a scale.Connect the water coolant of prolong, open electric heating cover and waste water is distilled.After steaming the waste water sample of 580ml, stop distillation.The pH value of the waste water steamed is 10.8, COD be 3320mg/L, B/C is 0.42.
Embodiment 4
The present embodiment is for illustration of the pretreatment process of described HTS factory effluent of the present invention.
Get the wastewater sample 1 shown in 600ml table 1, with sodium hydroxide, pH value is adjusted to 12, water sample is placed in the single port flask of 1000ml.Single port flask is placed on electric heating cover, and the outlet of single port flask is connected to snake type prolong, and the prolong the other end is connected to Erlenmeyer flask with a scale.Connect the water coolant of prolong, open electric heating cover and waste water is distilled.After steaming the waste water sample of 540ml, stop distillation.The pH value of the waste water steamed is 10.5, COD be 3720mg/L, B/C is 0.58.
Embodiment 5
The present embodiment is for illustration of the pretreatment process of described HTS factory effluent of the present invention.
Get the wastewater sample 1 shown in 600ml table 1, with sodium hydroxide, pH value is adjusted to 13, water sample is placed in the single port flask of 1000ml.Single port flask is placed on electric heating cover, and the outlet of single port flask is connected to snake type prolong, and the prolong the other end is connected to Erlenmeyer flask with a scale.Connect the water coolant of prolong, open electric heating cover and waste water is distilled.After steaming the waste water sample of 590ml, stop distillation.The pH value of the waste water steamed is 10.5, COD be 3250mg/L, B/C is 0.18.
Embodiment 6
The present embodiment is for illustration of the pretreatment process of described HTS factory effluent of the present invention.
Get the wastewater sample 2 shown in 600ml table 1, with sodium hydroxide, pH value is adjusted to 12.5, water sample is placed in the single port flask of 1000ml.Single port flask is placed on electric heating cover, and the outlet of single port flask is connected to snake type prolong, and the prolong the other end is connected to Erlenmeyer flask with a scale.Connect the water coolant of prolong, open electric heating cover and waste water is distilled.After steaming the waste water sample of 570ml, stop distillation.The pH value of the waste water steamed is 10.7, COD be 3220mg/L, B/C is 0.48.
As can be seen from the result of above-described embodiment 1-6, described method of the present invention is adopted to carry out pre-treatment to HTS factory effluent, make to obtain significant raising through the B/C of pretreated waste water, thus significantly improve the biodegradability of HTS factory effluent.
Claims (5)
1. a pretreatment process for HTS factory effluent, the method comprises: the pH value of described HTS factory effluent be adjusted to and be greater than 11, distilled the waste water obtained after adjust ph; The chemical oxygen demand (COD) of described HTS factory effluent is 21000-40000mg/L, and the ratio of biochemical oxygen demand (BOD) and chemical oxygen demand (COD) is less than 0.1.
2. method according to claim 1, wherein, is adjusted to 12-13 by the pH value of described HTS factory effluent.
3. method according to claim 1 and 2, wherein, the volume of the waste water steamed is the 80-99% of the volume of the waste water obtained after described adjust ph.
4. method according to claim 3, wherein, the volume of the waste water steamed is the 90-97% of the volume of the waste water obtained after described adjust ph.
5. method according to claim 1, wherein, the ratio of biochemical oxygen demand (BOD) and chemical oxygen demand (COD) is 0.01-0.08.
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