CN103130354A - Processing method for coal gasification waste water obtained through coal gasification - Google Patents
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Abstract
A processing method for coal gasification waste water obtained through coal gasification. The method comprises steps: under the condition of pressure gasification, contacting slack coal with water vapor and oxygen to obtain raw gas; contacting the raw gas with water to cool down and obtain a product of gas and liquid phase after purification, and separating oil and water of the liquid phase product to obtain the coal gasification waste water; processing the coal gasification waste water by deamination to obtain coal gasification waste water after the deamination; under the condition of supercritical of water, contacting the coal gasification waste water after the deamination with oxidant to obtain synthesis gas and waste water after contacting, wherein dosage of the oxidant is 0.2-0.8 times as much as oxygen demand of complete oxidation of organics and ammoniacal nitrogen in the coal gasification waste water after the deamination; biochemically processing the waste water obtained after contacting. The method can not only enable the content of organics of the coal gasification waste water to be reduced obviously, but also enable the organics of the coal gasification waste water to be converted into the synthesis gas, so that waste resource recovery is achieved.
Description
Technical field
The present invention relates to the treatment process of the coal gasification waste water that a kind of gasification obtains.
Background technology
Along with day being becoming tight of fossil energy especially oil supply, and use the increasingly serious of the environmental pollution that brings and global warming problem by fossil energy, the mankind are in the urgent need to changing traditional energy expenditure pattern and consumption structure.At present, the world energy sources consumption structure has completed the conversion from the solid energy to liquid energy, and starts to transform to Gas Energy Source, and the disposable energy expenditure of China still be take coal as main, and proportion is up to 70% left and right.For realizing the strategical adjustment of China's energy structure, the Filter Tuber For Clean Coal such as gasification utilizes technology to obtain broad development in recent years, and the exploitation of new forms of energy simultaneously also receives much concern.These low pollutions, applying of low emission technology meet current low-carbon economy Development patterns, are conducive to promote the transformation of Economic Growth in China mode.
In prior art, the main gasification that adopts prepares Sweet natural gas, the international coal preparing natural gas of big plain in u.s.a demonstration unit (20 years of operation) and the Datang project of take at present is representative, mainly adopt Shandong strange/crushed coal pressure gasifying, the oil resistant of anti-sulphur conversion, low-temperature rectisol purify and methanation.Typical process flow, for first the coal of extraction in colliery is carried out to the coal choosing, is divided into broken coal, coal dust and coal gangue, and broken coal is for pressurized gasification.The principal reaction of crushed coal pressure gasifying is coal and water generation water-gas reaction, and product is mainly carbon monoxide, hydrogen and methane, also has the undecomposed water of part, and a small amount of coal tar.The further methanation of carbon monoxide and hydrogen, obtain methane gas (being SNG).In the gas product of coal process for producing natural gained, the content of methane can be up to 96%, calorific value 35564kJ/m
3above.
But prepared in the Sweet natural gas process by above-mentioned employing gasification can discharge a large amount of harmful high-concentration coal gasification waste waters, 1 ton of coal of every gasification, coal gasification waste water output is 0.5～1.1m
3.On the one hand, in coal gasification waste water, the formation of organic substance has not only reduced total carbon gasification rate and the cold gas efficiency in the Coal Gasification Technology, and if can cause serious environmental pollution without effective processing; On the other hand, the large amount of organic contained in gasification has the potential quality of recycling.In addition, because the coal gasification waste water amount is large, if the direct discharge of the water after processing also can cause the waste of water resources, especially, when shortage water source, gas station location, when the consumption of fresh water is restricted, it is particularly urgent that the reuse of coal gasification waste water seems.
At present, the processing of coal gasification waste water adopts biology and chemical association technique more, but there are the defects such as secondary pollution, complex process, floor space be wide in technique itself, has seriously restricted degree of perfection and the technical superiority of Coal Gasification Technology.
In addition, in prior art, also have the people by overcritical complete oxidation technology for simulating the processing of coking chemical waste water, result shows that overcritical complete oxidation technology has good removal effect to phenol, ammonia nitrogen, effluent quality is better, can meet direct emission request.But this treatment process can not take full advantage of the organic resources in waste water.
Therefore, the processing reuse of coal gasification waste water has become an important topic in the urgent need to address in the resource and environment field.
Summary of the invention
The objective of the invention is is in order to overcome the above-mentioned defect of prior art, the treatment process of the coal gasification waste water that provides a kind of new gasification to obtain.
The invention provides the treatment process of the coal gasification waste water that a kind of gasification obtains, wherein, the method comprises the following steps:
1) under the pressurized gasification condition, broken coal is contacted with oxygen with water vapour, obtain a kind of raw gas, described raw gas contains naphtha fraction, diesel oil distillate and tarry cut;
2) coal gas and the liquid product by gained raw gas and water contact cooling, after being purified, carry out oily water separation by liquid product, obtains coal gasification waste water;
3) by step 2) in the coal gasification waste water obtained carry out the deamination processing, obtain the coal gasification waste water after deamination;
4) under the super critical condition of water, by step 3) in coal gasification waste water after the deamination that obtains contact the waste water after obtaining synthetic gas and contacting with oxygenant, the amount of described oxygenant is that in the coal gasification waste water after deamination organism and ammonia-state nitrogen be by the 0.2-0.8 of complete oxidation theoretical oxygen demand doubly;
5) by step 4) in waste water after the contact that obtains carry out biochemical treatment.
The treatment in accordance with the present invention method, not only can make the organic content in coal gasification waste water obviously reduce, and the organism in coal gasification waste water can be converted into to synthetic gas again, thereby realize that waste resource reclaims; And the waste water after processing can directly enter the routine biochemistry system and further be processed.
Embodiment
The invention provides the treatment process of the coal gasification waste water that a kind of gasification obtains, wherein, the method comprises the following steps:
1) under the pressurized gasification condition, broken coal is contacted with oxygen with water vapour, obtain a kind of raw gas, described raw gas contains naphtha fraction, diesel oil distillate and tarry cut;
2) coal gas and the liquid product by gained raw gas and water contact cooling, after being purified, carry out oily water separation by liquid product, obtains coal gasification waste water;
3) by step 2) in the coal gasification waste water obtained carry out the deamination processing, obtain the coal gasification waste water after deamination;
4) under the super critical condition of water, by step 3) in coal gasification waste water after the deamination that obtains contact the waste water after obtaining synthetic gas and contacting with oxygenant, the amount of described oxygenant be in the coal gasification waste water after deamination organism and ammonia-state nitrogen (also referred to as NH
3-N) by the 0.2-0.8 of complete oxidation theoretical oxygen demand doubly;
5) by step 4) in waste water after the contact that obtains carry out biochemical treatment.
In the present invention, organism in " organism and ammonia-state nitrogen are by the complete oxidation theoretical oxygen demand " can be with reference to the organism in existing chemical oxygen demand COD mensuration by the implication of complete oxidation by complete oxidation, and the mensuration of COD can be measured by the GB11914-89 dichromate titration.Ammonia-state nitrogen can ((or be claimed non-ionic ammonia, NH with free ammonia according to ammonia-state nitrogen by the complete oxidation theoretical oxygen demand
3) and ion ammonia (NH
4 +) nitrogen that exists of form) chemical equation that reacts generation nitrogen G&W with oxygen calculates, the mensuration of ammonia-state nitrogen can be measured by the method for GB/T 7481-1987.Described complete oxidation theoretical oxygen demand is interpreted as that oxygenant is the oxygen requirement under the present invention's oxygenant used.Be in the present invention, the consumption of oxygenant is calculated according to the COD value of the coal gasification waste water after deamination and ammonia nitrogen value.
The treatment in accordance with the present invention method, described coal gasification waste water contains water, phenol, ammonia and tar.In the present invention, to COD value and the NH of described coal gasification waste water
3-N value does not have special requirement.But from the coal gasification waste water source, consider, the COD value of preferred described coal gasification waste water is 10000-50000mg/L, NH
3-N value is 4500-17000mg/L; More preferably the COD value of coal gasification waste water is 14000-20000mg/L, NH
3-N value is 5000-12000.
The treatment in accordance with the present invention method, what coal gasification waste water was carried out to deamination can adopt this area routine carries out the deamination processing to remove the method for the ammonia in waste water to waste water, and described deamination is processed as long as meet and is made the NH in waste water
3-N value is to get final product below 400mg/L; To the COD value of the coal gasification waste water after deamination, there is no particular limitation, generally can, for below 30000mg/L, be preferably 7000-20000mg/L, more preferably 10000-15000mg/L.For example, can adopt the water vapour air lift to carry out deamination to coal gasification waste water, the method is conventionally known to one of skill in the art.Specifically, can be by water vapour and added in advance the coal gasification waste water of sodium hydroxide to be passed in gas stripping column to carry out air lift, the gas phase of generation is discharged from tower top, and the coal gasification waste water after deamination is discharged at the bottom of tower.Described air lift condition is well known in the art.
The treatment in accordance with the present invention method, the consumption of described oxygenant is extremely important.Described oxygenant can be selected by the complete oxidation theoretical oxygen demand according to organism and the ammonia-state nitrogen of the coal gasification waste water after deamination.Generally, the consumption of described oxygenant is that in the coal gasification waste water after deamination organism and ammonia-state nitrogen be by the 0.2-0.8 of complete oxidation theoretical oxygen demand doubly; In preferred situation, the consumption of described oxygenant be in the coal gasification waste water after deamination organism and ammonia-state nitrogen by the 0.3-0.6 of complete oxidation theoretical oxygen demand doubly, more preferably 0.4-0.6 doubly.
The treatment in accordance with the present invention method, generally, the super critical condition of described water comprises: temperature can be 24-27MPa for 400-600 ℃, pressure; In preferred situation, described temperature is that 430-500 ℃, pressure are 25-26.5MPa.
The treatment in accordance with the present invention method, contacting of oxygenant and coal gasification waste water after deamination can be carried out in the various devices that can produce supercritical water known in the field.Described device can be both the intermittent type device, can be also continuous reaction apparatus.
The treatment in accordance with the present invention method, in general situation, the time that described oxygenant contacts with coal gasification waste water after deamination can be 5-30 minute; The time that preferred described oxygenant contacts with coal gasification waste water after deamination is 8-15 minute.
The treatment in accordance with the present invention method, described oxygenant can be the various oxygenants that use in supercritical oxidation.In preferred situation, described oxygenant is oxygen and/or hydrogen peroxide.Described hydrogen peroxide can be take the hydrogen peroxide form that concentration is the 10-70 % by weight and be used.
The treatment in accordance with the present invention method, in order further to improve oxidation effectiveness, preferably in step 4) in by step 3) in coal gasification waste water and contacting under catalyzer exists of oxygenant after the deamination that obtains carry out.In the present invention, can with the fixed bed form, catalyzer be placed in to the top of supercritical reaction still, like this, under super critical condition, can make well step 3) in coal gasification waste water after the deamination that obtains with oxygenant, with catalyzer, contacted.
Above-mentioned catalyzer can be various catalyzer known in the field.Generally, described catalyzer can be various transition metal oxides known in the field, one or more in the oxide compound that more preferably described catalyzer is Cu, Co and Mn; More preferably CuO, Co
2o
3and MnO
2in one or more.The consumption of described catalyzer can be according to the weight of the coal gasification waste water after deamination and oxygenant, generally, gross weight in the coal gasification waste water after deamination and oxygenant, the consumption of described catalyzer is the 0.1-3.0 % by weight, be preferably the 0.5-2.0 % by weight, more preferably the 0.8-1.5 % by weight.
The method according to this invention, mainly contain hydrogen, carbon monoxide, methane and carbon dioxide in the synthetic gas of described generation, also contain a small amount of oxygen and nitrogen.
The method according to this invention, describedly can carry out gained raw gas and water contact cooling for the whole bag of tricks known in the field.Described contact can be once contact, can be also the substep contact.As long as coal gas and liquid product after being purified after making raw gas and the water contact cooling contacting, cooling temperature for example can for below 100 ℃ as 20-80 ℃ so that water is liquid, the low boiling components such as raw gas are gas.
The treatment in accordance with the present invention method, the described mode contacted with water can be the various cooling ways of contact, for example, can be counter current contact or and stream contact or the adverse current mode that also stream carries out simultaneously.
The method according to this invention, the preparation method of described raw gas can be method well known in the art, for example, can adopt crushed coal pressure gasifying method well known in the art to obtain.Described broken coal can be the various broken coal pieces that median size is not less than 5mm, the broken coal piece that for example median size is 2-50mm.Described pressurized gasification condition comprises that outlet raw gas temperature is 200-600 ℃, is preferably 300-500 ℃, and pressure can be 2-8MPa, is preferably 2-6MPa, more preferably 2-4MPa.Described pressurized gasification can carry out in various vapourizing furnaces known in the art, for example, in lurgi gasifier or crushed coal pressurized-gasification furnace, carries out.
The treatment in accordance with the present invention method, in step 1) described in the water vapor consumption can select according to the amount of broken coal, its usage ratio is well known in the art.The usage quantity of described oxygen can be selected according to the water vapor consumption, and the usage quantity of described oxygen can be the conventional amount of using in this area, and for example, with respect to the water vapor of 1kg, the usage quantity of described oxygen is 0.16-0.18Nm
3.
The treatment in accordance with the present invention method, what the method that the waste water after described contact is carried out to biochemical treatment can adopt this area routine carries out biochemical treatment to remove the organic method in waste water to waste water, the various conditions that the condition of described biochemical treatment can be commonly used for this area.Specifically, the method for described biochemical treatment can comprise the anaerobic-aerobic processing, wherein, the temperature of anaerobic treatment can be generally 35-40 ℃, the pH value can be 6-8, and sludge concentration can be 5-15g/L, and hydraulic detention time can be 3-4 days (reactor loads: 5-10kg (COD)/m
3d; Upper Flow Velocity: 3-5m/h; COD: N: P=350: 5: 1); The temperature of aerobic treatment can be generally 20-30 ℃, and the pH value can be 6-8, and the amount of dissolved oxygen can be 2-6mg/L, and sludge concentration can be 1-5g/L, and hydraulic detention time can be 1-2 days (COD: N: P=100: 5: 1).Wherein, described mud can be the anaerobic-aerobic active sludge of this area routine, and for example, described mud can be purchased from Shanghai Kangzhen Environmental Science & Technology Co., Ltd. together with anaerobic-aerobic equipment.
In the present invention, as one of them preferred version, described oxygenant is hydrogen peroxide, and the coal gasification waste water after the deamination with respect to every liter, and the consumption of oxygenant is the 4.7-8.9 gram.
Below by specific embodiment, the present invention is further detailed, but the present invention is not limited in following embodiment.
In following examples, the COD value of waste water adopts the GB11914-89 dichromate titration to measure; NH
3the mensuration of-N value adopts the method for GB/T 7481-1987 to carry out.
In following examples, the composition of synthetic gas adopts gas-chromatography to be measured, and its condition determination is as follows:
Detector: TCD detector
Chromatographic column: TDX-01 packed column (3m * 3m)
Carrier gas: helium, pressure 0.42MPa before post, flow velocity 18.5ml/min
Temperature: 50 ℃ of chromatographic columns, 60 ℃ of TCD detectors.
Embodiment 1
The present embodiment is for illustrating the treatment process of the coal gasification waste water that gasification provided by the invention obtains.
1) (relevant physical property refers to table 1 to the brown coal broken coal that is 5-50mm by median size, below identical) add vapourizing furnace by furnace roof through coal lock, water vapor and oxygen are entered from the stove below respectively, wherein, the weight ratio of broken coal and water vapor is 0.7: 1, with respect to the water vapor of 1kg, the oxygen inlet is 0.18Nm
3.The bottom temp of vapourizing furnace is 1200 ℃, and head temperature is 500 ℃, and base pressure is 3.5MPa, and top pressure is 3MPa, and obtaining pressure is that the crushed coal pressure gasifying product that 3MPa, temperature are 500 ℃ discharges from top of gasification furnace containing the gas mixture of tar.
2) by this pressure, be then 3MPa, the crushed coal pressure gasifying product that temperature is 500 ℃ be take flow and the temperature of 1000 kg/hrs and is 200 ℃, the water that flow is 800 kg/hrs contacts and carries out chilling in the chilling separator, contact after 25 seconds, make the temperature of described raw gas be reduced to 220 ℃, obtain the first gas-phase product and the first liquid product, the first gas-phase product further is cooled to 190 ℃, obtain the second gas-phase product and second liquid phase product, the second gas-phase product is cooled to 30 ℃ again, coal gas after being purified and the 3rd liquid product, by the first liquid product, second liquid phase product and the 3rd liquid product carry out oily water separation after mixing, (the COD value is 19310mg/L to obtain coal gasification waste water, NH
3-N value is 7500mg/L).
3) by 120 ℃, water vapour and the step 2 of 0.2MPa) in obtain coal gasification waste water (adding 0.3 % by weight sodium hydroxide), pass into respectively in gas stripping column and carry out the air lift deamination, 120 ℃ of column bottom temperatures, 100 ℃ of tower top temperatures, water vapor and coal gasification waste water weight ratio are 0.8: 1, the gas phase produced is discharged by tower top, and the coal gasification waste water after deamination is discharged at the bottom of tower.The water quality of the coal gasification waste water after this deamination is in Table 2.
4) by the coal gasification waste water after deamination and hydrogen peroxide (H
2o
2concentration is 30 % by weight, this waste water of 1L is used the hydrogen peroxide of 29.5g, be equivalent in the coal gasification waste water after deamination organism and ammonia-state nitrogen by 0.6 times of the complete oxidation theoretical oxygen demand) mix after, join in reactor, be under 430 ℃, the pressure condition that is 25MPa in temperature, react 10 minutes.By the reactor outlet material is cooling be decompressed to normal temperature and pressure after, enter gas-liquid separator, synthetic gas is discharged by the gas-liquid separator top, the waste water after processing is from the discharge of separator bottom.Effluent quality is shown in Table 2, and the amount of gas composition and every milliliter of coal gasification waste water generation synthetic gas is shown in Table 3.
5) waste water after processing is sent into purchased from further carrying out the anaerobic-aerobic processing in the anaerobic-aerobic equipment of Shanghai Kangzhen Environmental Science & Technology Co., Ltd., the temperature of anaerobic treatment is 35 ℃, the pH value is 7, sludge concentration is 10g/L, and hydraulic detention time is 3 days (reactor load: 9kg (COD)/m
3d; Upper Flow Velocity: 4m/h; COD: N: P=350: 5: 1); The temperature of aerobic treatment is 20 ℃, and the pH value is 7, and the amount of dissolved oxygen is 5mg/L, and sludge concentration is 3g/L, and hydraulic detention time can be 1 day (COD: N: P=100: 5: 1), and the water quality of the waste water after the biochemical treatment obtained is in Table 2.
Embodiment 2
The present embodiment is for illustrating the treatment process of the coal gasification waste water that gasification provided by the invention obtains.
1) the brown coal broken coal that is 5-50mm by median size adds vapourizing furnace by furnace roof through the coal lock, and water vapor and oxygen are entered from the stove below respectively, and wherein, the weight ratio of broken coal and water vapor is 0.7: 1, and with respect to the water vapor of 1kg, the oxygen inlet is 0.18Nm
3.The bottom temp of vapourizing furnace is 1200 ℃, and head temperature is 500 ℃, and base pressure is 3.5MPa, and top pressure is 3MPa, and obtaining pressure is that the crushed coal pressure gasifying product that 3MPa, temperature are 500 ℃ discharges from top of gasification furnace containing the gas mixture of tar.
2) by this pressure, be then 3MPa, the crushed coal pressure gasifying product that temperature is 500 ℃ be take flow and the temperature of 1000 kg/hrs and is 200 ℃, the water that flow is 800 kg/hrs contacts and carries out chilling in the chilling separator, contact after 25 seconds, make the temperature of described raw gas be reduced to 220 ℃, obtain the first gas-phase product and the first liquid product, the first gas-phase product further is cooled to 190 ℃, obtain the second gas-phase product and second liquid phase product, the second gas-phase product is cooled to 40 ℃ again, coal gas after being purified and the 3rd liquid product, by the first liquid product, second liquid phase product and the 3rd liquid product carry out oily water separation after mixing, (the COD value is 14500mg/L to obtain coal gasification waste water, NH
3-N value is 5200mg/L).
3) by 120 ℃, water vapour and the step 2 of 0.2MPa) in obtain coal gasification waste water (adding 0.3 % by weight sodium hydroxide), pass into respectively in gas stripping column and carry out air lift, 120 ℃ of column bottom temperatures, 100 ℃ of tower top temperatures, water vapor and waste water weight ratio are 0.8: 1, the gas phase produced is discharged by tower top, and the coal gasification waste water after deamination is discharged at the bottom of tower.The water quality of the coal gasification waste water after this deamination is in Table 2.
4) by the coal gasification waste water after deamination and hydrogen peroxide (H
2o
2concentration is 30 % by weight, this waste water of 1L is used the hydrogen peroxide of 15.7g, be equivalent in the coal gasification waste water after deamination organism and ammonia-state nitrogen by 0.4 times of the complete oxidation theoretical oxygen demand) mix after, join in reactor, be under 450 ℃, the pressure condition that is 25MPa in temperature, react 15 minutes.The reactor outlet material is cooling be decompressed to normal temperature and pressure after, enter gas-liquid separator, synthetic gas is discharged by the gas-liquid separator top, the waste water water after processing is from the discharge of separator bottom.Effluent quality is shown in Table 2, and the amount of gas composition and every milliliter of coal gasification waste water generation synthetic gas is shown in Table 3.
5) waste water after processing is further sent in the anaerobic-aerobic equipment purchased from Shanghai Kangzhen Environmental Science & Technology Co., Ltd. and carried out the anaerobic-aerobic processing, the temperature of anaerobic treatment is 35 ℃, the pH value is 7, sludge concentration is 10g/L, and hydraulic detention time is 4 days (reactor load: 9kg (COD)/m
3d; Upper Flow Velocity: 5m/h; COD: N: P=350: 5: 1); The temperature of aerobic treatment is 20 ℃, and the pH value is 7, and the amount of dissolved oxygen is 5mg/L, and sludge concentration is 3g/L, and hydraulic detention time is 2 days (COD: N: P=100: 5: 1), and the water quality of the waste water after the biochemical treatment obtained is in Table 2.
Embodiment 3
The present embodiment is for illustrating the treatment process of the coal gasification waste water that gasification provided by the invention obtains.
According to the method in embodiment 1, carry out, different is in step 4) in the coal gasification waste water after deamination and hydrogen peroxide are mixed after, join in reactor, with the fixed bed form, Catalysts Cu O is placed in to the top of reactor, wherein, in the gross weight of the coal gasification waste water after deamination and hydrogen peroxide, the consumption of catalyzer is 0.8 % by weight, and the reaction times is 8 minutes.The water quality of the coal gasification waste water after deamination, the waste water after first supercritical processing and the waste water after biochemical treatment is shown in Table 2, and the amount of gas composition and every milliliter of coal gasification waste water generation synthetic gas is shown in Table 3.
Embodiment 4
The present embodiment is for illustrating the treatment process of the coal gasification waste water that gasification provided by the invention obtains.
According to the method in embodiment 1, carry out, different is in step 4) in the coal gasification waste water after deamination and hydrogen peroxide are mixed after, join in reactor, with the fixed bed form by CATALYST Co
2o
3be placed in the top of reactor, wherein, in the gross weight of the coal gasification waste water after deamination and hydrogen peroxide, the consumption of catalyzer is 1 % by weight, and the reaction times is 8 minutes.The water quality of the coal gasification waste water after deamination, the waste water after first supercritical processing and the waste water after biochemical treatment is shown in Table 2, and the amount of gas composition and every milliliter of coal gasification waste water generation synthetic gas is shown in Table 3.
Embodiment 5
The present embodiment is for illustrating the treatment process of the coal gasification waste water that gasification provided by the invention obtains.
According to the method in embodiment 1, carry out, different is in step 4) in the coal gasification waste water after deamination and hydrogen peroxide are mixed after, join in reactor, with the fixed bed form by catalyzer MnO
2be placed in the top of reactor, wherein, in the gross weight of the coal gasification waste water after deamination and hydrogen peroxide, the consumption of catalyzer is 1.5 % by weight, and the reaction times is 8 minutes.The water quality of the coal gasification waste water after deamination, the waste water after first supercritical processing and the waste water after biochemical treatment is shown in Table 2, and the amount of gas composition and every milliliter of coal gasification waste water generation synthetic gas is shown in Table 3.
Table 1
Annotate:
War---mean coal-fired moisture as received coal; Wad---mean coal-fired dry base moisture; Har---mean that coal-fired as received basis hydrogen divides; Aad---mean coal-fired dry base ash content; Vad---mean coal-fired dry base volatile matter; Sad---mean coal-fired dry base sulphur content; Car---mean that coal-fired as received basis carbon divides; Oar---mean that coal-fired as received basis oxygen divides; Nar---mean that coal-fired as received basis nitrogen divides; Sar---mean coal-fired as received basis sulphur content; T1---softening temperature, ℃; T2---hemispherical temperature, ℃; T3---melt temperature, ℃.
Table 2
Table 3
By table 2 and table 3, can find out, the method according to this invention, not only can reduce the organic content in coal gasification waste water effectively, reduces the COD value of coal gasification waste water, and can generate synthetic gas in the COD value that reduces coal gasification waste water, realize the waste resource recycling.
Claims (13)
1. the treatment process of the coal gasification waste water that a gasification obtains, is characterized in that, the method comprises the following steps:
1) under the pressurized gasification condition, broken coal is contacted with oxygen with water vapour, obtain a kind of raw gas, described raw gas contains naphtha fraction, diesel oil distillate and tarry cut;
2) coal gas and the liquid product by gained raw gas and water contact cooling, after being purified, carry out oily water separation by liquid product, obtains coal gasification waste water;
3) by step 2) in the coal gasification waste water obtained carry out the deamination processing, obtain the coal gasification waste water after deamination;
4) under the super critical condition of water, by step 3) in coal gasification waste water after the deamination that obtains contact the waste water after obtaining synthetic gas and contacting with oxygenant, the consumption of described oxygenant is that in the coal gasification waste water after deamination organism and ammonia-state nitrogen be by the 0.2-0.8 of complete oxidation theoretical oxygen demand doubly;
5) by step 4) in waste water after the contact that obtains carry out biochemical treatment.
2. treatment process according to claim 1, wherein, the consumption of described oxygenant is that in the coal gasification waste water after deamination organism and ammonia-state nitrogen be by the 0.3-0.6 of complete oxidation theoretical oxygen demand doubly.
3. the time that treatment process according to claim 1, wherein, step 4), oxygenant contacts with coal gasification waste water after deamination is 5-30 minute.
4. the time that treatment process according to claim 3, wherein, step 4), oxygenant contacts with coal gasification waste water after deamination is 8-15 minute.
5. treatment process according to claim 1, wherein, the super critical condition of described water comprises: temperature is that 400-600 ℃, pressure are 24-27MPa.
6. according to the described treatment process of claim 1-4 any one, wherein, described oxygenant is oxygen and/or hydrogen peroxide.
7. treatment process according to claim 1, wherein, the COD value of described coal gasification waste water is 10000-50000mg/L, NH
3-N value can be 4500-17000mg/L.
8. treatment process according to claim 1, wherein, the NH of the coal gasification waste water after described deamination
3-N value is less than 400mg/L.
9. according to the described treatment process of claim 1 or 8, wherein, described oxygenant is hydrogen peroxide, and the coal gasification waste water after the deamination with respect to every liter, and the consumption of oxygenant is the 4.7-8.9 gram.
10. according to the described treatment process of any one in claim 1-9, wherein, in step 4) in by step 3) in coal gasification waste water and contacting under catalyzer exists of oxygenant after the deamination that obtains carry out.
11. treatment process according to claim 10, wherein, described catalyzer is transition metal oxide; In the gross weight of the coal gasification waste water after deamination and oxygenant, the consumption of described catalyzer is the 0.1-3.0 % by weight.
12. treatment process according to claim 1, wherein, step 1) described in, the broken coal median size is 2-50mm.
13. treatment process according to claim 1, wherein, the condition of described pressurized gasification comprises that gas outlet temperature is 200-600 ℃, and pressure is 2-8MPa.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104004557A (en) * | 2014-03-05 | 2014-08-27 | 新疆龙宇能源准东煤化工有限责任公司 | Method for producing coal-based natural gas through crushed coal pressurized gasification combined with water-coal slurry gasification |
| CN105948306A (en) * | 2016-05-12 | 2016-09-21 | 华陆工程科技有限责任公司 | Pretreatment and comprehensive utilization method of wastewater and waste gas produced during coal gasification |
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| JPH10226791A (en) * | 1997-02-17 | 1998-08-25 | Hitachi Ltd | Apparatus for treating trace metal |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004557A (en) * | 2014-03-05 | 2014-08-27 | 新疆龙宇能源准东煤化工有限责任公司 | Method for producing coal-based natural gas through crushed coal pressurized gasification combined with water-coal slurry gasification |
| CN104004557B (en) * | 2014-03-05 | 2016-02-10 | 新疆龙宇能源准东煤化工有限责任公司 | Crushed coal pressure gasifying associating coal water slurry gasification produces the method for coal preparing natural gas |
| CN105948306A (en) * | 2016-05-12 | 2016-09-21 | 华陆工程科技有限责任公司 | Pretreatment and comprehensive utilization method of wastewater and waste gas produced during coal gasification |
| 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 |
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| CN103130354B (en) | 2015-05-27 |
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