CN104058538B - A kind of processing method of wastewater stripping depickling deamination - Google Patents
A kind of processing method of wastewater stripping depickling deamination Download PDFInfo
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- CN104058538B CN104058538B CN201410310223.8A CN201410310223A CN104058538B CN 104058538 B CN104058538 B CN 104058538B CN 201410310223 A CN201410310223 A CN 201410310223A CN 104058538 B CN104058538 B CN 104058538B
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Abstract
The present invention relates to the processing method of the reduction of discharging of a kind of trade effluent and recycling, specifically relating to one adopts High efficiency stripping deamination technique and the process of stripping deacidifying process containing ammonia acid-bearing wastewater, and the ammonia nitrogen in waste water and hydrogen sulfide is carried out to the method for recycling.The waste water of ammonia-nitrogen content 500-50000mg/L and hydrogen sulfide content 100 ~ 10000mg/L can reach country-level ammonia nitrogen emission standard after art breading provided by the invention, and sulfide content is down to below 20mg/L; Ammonia simultaneously in waste water is recycled with the form of highly purified ammonium sulfate, and the hydrogen sulfide removed in waste water can be used for producing sulphur.
Description
Technical field
The present invention relates to the method for the reduction of discharging of a kind of trade effluent and recycling, specifically relate to a kind of energy-efficient stripping deamination technique and stripping deacidifying process combination treatment of adopting containing ammonia acid-bearing wastewater, and the ammonia nitrogen in waste water and hydrogen sulfide are carried out to the method for recycling.
Background technology
The ammonia nitrogen waste water of the acid gas components such as a large amount of sulfide hydrogen and carbonic acid gas can be produced, if do not carry out process to it can cause high risks to environment in the industry production such as Coal Chemical Industry and petrochemical complex process.External process high density is containing sewage many employings vaporizing extract process of ammonia at present, as US Patent No. 3335071 and US3404072, and domestic have adopt Single-tower stripping lateral line withdrawal function technical finesse sulfur-bearing containing ammonia sewage, as ZL97115113.X, its common feature be consume energy higher, process waste water per ton and need steam about 140 ~ 180 kilograms, and NH_3-N treating scope is narrower, water outlet ammonia nitrogen concentration does not reach national grade one discharge standard (GB8978-1996 " integrated wastewater discharge standard " regulation primary standard ammonia nitrogen is less than 15mg/L).For the waste water containing acid containing ammonia, the stripping deacidifying process that this patent adopts and stripping deamination technique, good energy-conserving effect, can reach good depickling deamination effect, and recyclable highly purified ammonium sulfate is used as nitrogenous fertilizer, and isolates hydrogen sulfide for sulphur processed.
This patent, based on efficient energy-saving coupling stripping deamination technology ZL201010507488.9, improves further on its basis and contains ammonia acid-bearing wastewater for the treatment of what produce in Coal Chemical Industry and oil refining industry, reach the object of energy-saving and emission-reduction and recycling.
Summary of the invention
The present invention relates to the method for the reduction of discharging of a kind of trade effluent and recycling, specifically relate to a kind of High efficiency stripping deamination technique and stripping deacidifying process combination treatment of adopting containing ammonia acid-bearing wastewater, and the ammonia nitrogen in waste water and hydrogen sulfide are carried out to the method for recycling.The processing method that the present invention adopts comprises equipment array mode and implementation method two aspect.
Processing unit combination explanation
The invention provides the processing unit array mode of a kind of process containing ammonia acid-bearing wastewater, it is characterized in that in processing unit at least containing capital equipment unit such as inlet outlet heat exchanger, stripping extracting tower, steam stripping ammonia-removing tower, ammonia absorption tower, condenser, ammoniumsulphate soln storage tank and evaporative crystallizers; Its array mode is as follows:
The pending ammonia acid-bearing wastewater liquid storage tank that contains is connected with stripping extracting tower waterwater entrance through the tube side of inlet outlet heat exchanger; The shell side of inlet outlet heat exchanger exports with steam stripping ammonia-removing tower still bottom outlet and processed waste water and is connected.
Bottom stripping extracting tower tower reactor, delivery conduit is connected by the pipeline of triplate line with input sodium hydroxide solution, and the delivery port of triplate line is connected by the liquid distributor of pump with steam stripping ammonia-removing tower stripping deamination section upper end; Between stripping extracting tower tower reactor with stripping depickling section, gas phase entrance to be exported with steam stripping ammonia-removing tower top gas phase by pipeline and is connected; Have liquid distributor between stripping extracting tower stripping depickling Duan Yuqi tower top, the intake line of liquid distributor is connected with the condenser reflux mouth on ammonia absorption tower top; Stripping extracting tower tower top outlet is connected with the gas phase input aperture between ammonia absorption tower absorber portion and tower reactor by pipeline.
Be connected with ammoniumsulphate soln storage tank by pipeline bottom ammonia absorption tower tower reactor, ammoniumsulphate soln outlet exports solid ammonium sulfate by evaporative crystallizer, input evaporative crystallizer steam at the secondary steam produced after evaporative crystallizer through Cemented filling between steam stripping ammonia-removing tower stripping deamination section and steam stripping ammonia-removing tower tower reactor; Liquid distributor between ammonia absorption tower absorber portion with its tower top is connected by the storage tank of pipeline with input dilute sulphuric acid, the outlet of ammonia absorption tower top gaseous phase is divided into two-way after condenser cooling, concentrated acid gas is discharged to subsequent disposal workshop section in one tunnel, and another road phlegma is back between stripping extracting tower stripping stage and tower top.
The outlet of steam stripping ammonia-removing tower top gaseous phase is connected with the gas phase entrance between tower reactor with stripping extracting tower stripping stage; Steam stripping ammonia-removing tower tower top is connected with the outlet of stripping extracting tower tower reactor and the pipeline of sodium hydroxide solution entrance through pump with the liquid distributor between stripping stage; Gas phase entrance between steam stripping ammonia-removing tower stripping deamination section and tower reactor thereof is connected with the secondary steam output channel of steam input pipe road and ammoniumsulphate soln evaporative crystallizer; The outlet of steam stripping ammonia-removing tower tower reactor is connected through the wastewater outlet of inlet outlet heat exchanger shell side after process.
Process implementing method
The present invention adopts the combination unit of above-mentioned processing unit to carry out deamination depickling process to containing ammonia acid-bearing wastewater, and reclaims the ammonia removed and hydrogen sulfide, and the process implementing method for this reason adopted comprises:
What need process inputs in stripping extracting tower after the dispersion of stripping depickling Duan Shangjing liquid distributor containing ammonia acid-bearing wastewater after waste water pump is heated up by inlet outlet heat exchanger, and the ammonia steam that contains exporting stripping extracting tower in stripping depickling section and steam stripping ammonia-removing tower gaseous phase outlet to carries out refluent heat/matter transmission; Hydrogen sulfide in waste water and carbonic acid gas, and small part ammonia enters vapor phase, ammonia-containing water after depickling is discharged after sodium hydroxide solution adjusted to ph from tower reactor, sprayed to steam stripping ammonia-removing tower stripping deamination section upper end by pump delivery, ammonia-containing water meets at the secondary steam that live steam and the evaporative crystallizer of stripping deamination section and feeding feed back and carries out refluent heat/matter transmission, ammonia enters vapor phase in the process, realizes the object of deamination.Export from tower reactor after waste water deaminizing, discharge through inlet outlet heat exchanger and untreated containing after sour ammonia-containing water heat exchange.Stripping extracting tower stripping depickling section is inputed to for stripping depickling by steam stripping ammonia-removing tower tower top containing ammonia steam; That discharges from stripping extracting tower tower top is transported to ammonia absorption tower containing ammonia containing acid vapour, in ammonia absorption tower ammonia absorber portion and the dilute sulphuric acid counter current contact sprayed, ammonia is absorbed generation ammoniumsulphate soln by dilute sulphuric acid and collects in tower reactor, liquid storage in tower reactor is delivered to sulfuric acid sparger cyclic absorption ammonia by sulfuric acid pump, saturated ammonium sulphate solution is regularly discharged to storage tank by self-con-tained unit, and in vapo(u)rization system, reclaiming solid ammonium sulfate and secondary steam further, secondary steam is transported to steam stripping ammonia-removing tower and again utilizes; Remove and to be delivered to condenser condensation from ammonia absorption tower top except water vapour containing acid vapour after ammonia, what condensation obtained is back to stripping extracting tower stripping depickling section spray containing acid condensation liquid, from carbonic acid gas and hydrogen sulfide mixed gas that the gas phase of condenser discharge is high density, aftertreatment can be carried out for recovery sulphur.
Significant improvement of the present invention comprises:
According to the difference of sour gas and ammonia at high temperature volatility, by stripping extracting tower and steam stripping ammonia-removing tower serial operation, take full advantage of system thermal;
Change conventional deacidification tower top cold feed into hot feed, reduce System steam unit consumption;
Before deacidification process makes deamination operation prior to deamination operation, waste water alkalescence improves, and reduces the consumption of the sodium hydroxide regulating waste water potential of hydrogen;
Significantly reduce system operation cost by above-mentioned improvement, reach energy-conservation effect.
Accessible beneficial effect after the invention process:
(1) per hour accessible containing ammonia acid-bearing wastewater amount: 1t and more than;
(2) ammonia-nitrogen content in waste water can be processed: 500 ~ 50000mg/L;
(3) after process, in waste discharge, ammonia-nitrogen content is low: 1 ~ 10mg/L (lower than national grade one discharge standard 15mg/L);
(4) hydrogen sulfide content in waste water can be processed: 100 ~ 10000mg/L;
(5) hydrogen sulfide content after process in waste discharge: be less than 20mg/L;
(6) steam consumption quantity needed for waste water per ton: be less than 150kg;
(7) product is reclaimed: high-purity sulfuric acid ammonium and hydrogen sulfide are for sulphur processed.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of wastewater stripping depickling deamination technique.
concrete case study on implementation
Below enumerate embodiment to further illustrate embodiment of the present invention.But the present invention is not limited to following embodiment.
Embodiment 1
Adopt process of the present invention containing ammonia acid-bearing wastewater import ammonia nitrogen concentration 1800mg/L, sulfide concentration 780mg/L, treatment capacity is 1m
3/ h.Reagent colorimetric method (GB7479-87) and sub-methyl blue spectrum analysis (GB/T16489-1996) is adopted to analyze, ammonia nitrogen concentration in processed waste water is 2.7mg/L, hydrogen sulfide content is 5mg/L, and steam consumption is 132kg/ ton waste water.
Embodiment 2
Adopt process of the present invention containing ammonia acid-bearing wastewater import ammonia nitrogen concentration 10100mg/L, sulfide concentration 6400mg/L, treatment capacity is 120m
3/ h.Reagent colorimetric method (GB7479-87) and sub-methyl blue spectrum analysis (GB/T16489-1996) is adopted to analyze, ammonia nitrogen concentration in processed waste water is 8.0mg/L, hydrogen sulfide content is 14mg/L, and steam consumption is 120kg/ ton waste water.
Embodiment 3
Adopt process of the present invention containing ammonia acid-bearing wastewater import ammonia nitrogen concentration 38300mg/L, sulfide concentration 1500mg/L, treatment capacity is 30m
3/ h.Reagent colorimetric method (GB7479-87) and sub-methyl blue spectrum analysis (GB/T16489-1996) is adopted to analyze, ammonia nitrogen concentration in processed waste water is 6.5mg/L, hydrogen sulfide content is 13mg/L, and steam consumption is 126kg/ ton waste water.
Claims (2)
1. process is containing a processing method for ammonia acid-bearing wastewater, and its feature is to adopt following equipment and array mode:
A. major equipment comprises: inlet outlet heat exchanger, stripping extracting tower, steam stripping ammonia-removing tower, ammonia absorption tower, condenser, ammoniumsulphate soln storage tank and evaporative crystallizer;
B. the array mode of equipment employing:
The pending ammonia acid-bearing wastewater liquid storage tank that contains is connected with stripping extracting tower waterwater entrance through the tube side of inlet outlet heat exchanger; The shell side of inlet outlet heat exchanger exports with steam stripping ammonia-removing tower still bottom outlet and processed waste water and is connected;
Bottom stripping extracting tower tower reactor, delivery conduit is connected by the pipeline of triplate line with input sodium hydroxide solution, and the delivery port of triplate line is connected by the liquid distributor of pump with steam stripping ammonia-removing tower stripping deamination section upper end; Between stripping extracting tower tower reactor with stripping depickling section, gas phase entrance to be exported with steam stripping ammonia-removing tower top gas phase by pipeline and is connected; Have liquid distributor between stripping extracting tower stripping depickling Duan Yuqi tower top, the intake line of liquid distributor is connected with the condenser reflux mouth on ammonia absorption tower top; Stripping extracting tower tower top outlet is connected with the gas phase input aperture between ammonia absorption tower absorber portion and tower reactor by pipeline;
Be connected with ammoniumsulphate soln storage tank by pipeline bottom ammonia absorption tower tower reactor, ammoniumsulphate soln outlet exports solid ammonium sulfate by evaporative crystallizer, input evaporative crystallizer steam at the secondary steam produced after evaporative crystallizer through Cemented filling between steam stripping ammonia-removing tower stripping deamination section and steam stripping ammonia-removing tower tower reactor; Liquid distributor between ammonia absorption tower absorber portion with its tower top is connected by the storage tank of pipeline with input dilute sulphuric acid, the outlet of ammonia absorption tower top gaseous phase is divided into two-way after condenser cooling, concentrated acid gas is discharged to subsequent disposal workshop section in one tunnel, and another road phlegma is back between stripping extracting tower stripping stage and tower top;
The outlet of steam stripping ammonia-removing tower top gaseous phase is connected with the gas phase entrance between tower reactor with stripping extracting tower stripping stage; Steam stripping ammonia-removing tower tower top is connected with the outlet of stripping extracting tower tower reactor and the pipeline of sodium hydroxide solution entrance through pump with the liquid distributor between stripping stage; Gas phase entrance between steam stripping ammonia-removing tower stripping deamination section and tower reactor thereof is connected with the secondary steam output channel of steam input pipe road and ammoniumsulphate soln evaporative crystallizer; The outlet of steam stripping ammonia-removing tower tower reactor is connected through the wastewater outlet of inlet outlet heat exchanger shell side after process.
2. process is containing a processing method for ammonia acid-bearing wastewater, it is characterized in that adopting the equipment in claim 1 and array mode thereof, and adopts following processing step:
What need process inputs in stripping extracting tower after the dispersion of stripping depickling Duan Shangjing liquid distributor containing ammonia acid-bearing wastewater after waste water pump is heated up by inlet outlet heat exchanger, and the ammonia steam that contains exporting stripping extracting tower in stripping depickling section and steam stripping ammonia-removing tower gaseous phase outlet to carries out refluent heat/matter transmission; Hydrogen sulfide in waste water and carbonic acid gas, and small part ammonia enters vapor phase, ammonia-containing water after depickling is discharged after sodium hydroxide solution adjusted to ph from tower reactor, sprayed to steam stripping ammonia-removing tower stripping deamination section upper end by pump delivery, ammonia-containing water meets at the secondary steam that live steam and the evaporative crystallizer of stripping deamination section and feeding feed back and carries out refluent heat/matter transmission, ammonia enters vapor phase in the process, realizes the object of deamination; Export from tower reactor after waste water deaminizing, discharge through inlet outlet heat exchanger and untreated containing after sour ammonia-containing water heat exchange; Stripping extracting tower stripping depickling section is inputed to for stripping depickling by steam stripping ammonia-removing tower tower top containing ammonia steam; That discharges from stripping extracting tower tower top is transported to ammonia absorption tower containing ammonia containing acid vapour, in ammonia absorption tower ammonia absorber portion and the dilute sulphuric acid counter current contact sprayed, ammonia is absorbed generation ammoniumsulphate soln by dilute sulphuric acid and collects in tower reactor, liquid storage in tower reactor is delivered to sulfuric acid sparger cyclic absorption ammonia by sulfuric acid pump, saturated ammonium sulphate solution is regularly discharged to storage tank by self-con-tained unit, and in vapo(u)rization system, reclaiming solid ammonium sulfate and secondary steam further, secondary steam is transported to steam stripping ammonia-removing tower and again utilizes; Remove and to be delivered to condenser condensation from ammonia absorption tower top except water vapour containing acid vapour after ammonia, what condensation obtained is back to stripping extracting tower stripping depickling section spray containing acid condensation liquid, from carbonic acid gas and hydrogen sulfide mixed gas that the gas phase of condenser discharge is high density, carry out aftertreatment for recovery sulphur.
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| CN104478026B (en) * | 2014-12-12 | 2016-08-24 | 北京阳光欣禾科技有限公司 | Coupling energy-saving stripping deamination process in a kind of |
| CN205347077U (en) * | 2015-09-23 | 2016-06-29 | 北方稀土生一伦高科技有限公司 | Handle device of ammonium chloride waste water |
| CN105948306B (en) * | 2016-05-12 | 2018-09-21 | 华陆工程科技有限责任公司 | A kind of pretreatment of coal gasification waste water exhaust gas and method of comprehensive utilization |
| CN105948153B (en) * | 2016-05-25 | 2018-09-07 | 中科瑞奥能源科技股份有限公司 | Phenol ammonia waste water processing and utilizing system and technique |
| CN106315726B (en) * | 2016-10-12 | 2019-05-03 | 江苏金茂源生物化工有限责任公司 | A kind of biogas slurry decarburization combining deamination system |
| NL2020788B1 (en) | 2017-04-21 | 2019-06-26 | China Petroleum & Chem Corp | Apparatus and Method for Treating Waste Water Containing Ammonium Salts |
| CN107129087B (en) * | 2017-05-04 | 2020-11-10 | 北京阳光欣禾科技有限公司 | Process method for removing ammonia and chromium from garbage penetrating fluid |
| CN107324284B (en) * | 2017-07-07 | 2020-01-14 | 天津市职业大学 | System for resourcefully handle useless hydrochloric acid of iron-containing industry |
| CN109704366B (en) * | 2019-02-11 | 2023-08-01 | 中冶焦耐(大连)工程技术有限公司 | A heat coupling process and system for pressurized deacidification and ammonia distillation |
| CN110104712A (en) * | 2019-04-19 | 2019-08-09 | 中石化宁波工程有限公司 | A kind of Treatment Method of Ammonia-contained Waste Water |
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| JPH11114552A (en) * | 1997-10-20 | 1999-04-27 | Kurita Water Ind Ltd | Recovery of valuables from organic wastewater |
| CN102190341B (en) * | 2010-03-09 | 2012-12-26 | 中国石油化工股份有限公司 | Stripping ammonia-removing method based on flash evaporation and heat pump technologies |
| CN102030386B (en) * | 2010-10-15 | 2012-02-01 | 北京化工大学 | A high-efficiency energy-saving coupling stripping deamination equipment and method |
| CN102320671B (en) * | 2011-06-17 | 2013-01-30 | 青岛科技大学 | A kind of treatment method of waste water containing acid and ammonia |
| CN102863112A (en) * | 2012-10-19 | 2013-01-09 | 天津市昊永化工科技有限公司 | Phenol and ammonia wastewater recycling treatment method by using single tower for performing de-acidification and de-amination simultaneously |
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