CN109485190A - The processing method and gasification of coal and its system in the Heisui River that coal gasification generates - Google Patents
The processing method and gasification of coal and its system in the Heisui River that coal gasification generates Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
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- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C02F1/02—Treatment of water, waste water, or sewage by heating
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- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
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- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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Abstract
The present invention relates to coal gasification industrial circles, and in particular, to the processing method and gasification of coal and its system in the Heisui River that a kind of coal gasification generates.The processing method includes: Heisui River to be carried out high pressure flash, and the Heisui River after high pressure flash is carried out eddy flow except solid processing；Resulting top clear stream successively carries out low pressure flash and vacuum flashing after the eddy flow is removed solid processing；By after the vacuum flashing Heisui River and the eddy flow except after solid processing resulting bottom concentrated water carry out settlement treatment；Supernatant obtained by the settlement treatment and calcium hydroxide and sodium carbonate are subjected to haptoreaction；In the presence of flocculant, the Heisui River after the haptoreaction is subjected to flocculation treatment；Heisui River after the flocculation treatment is settled, sedimentation gained supernatant is successively filtered processing and electrodialysis process.By using the processing method in the Heisui River that coal gasification of the invention generates, the hardness in Heisui River can be greatly reduced, corrosive salt is effectively removed.
Description
Technical field
The present invention relates to coal gasification industrial circles, and in particular, to a kind of processing method in the Heisui River that coal gasification generates and
Gasification of coal and its system.
Background technique
The Heisui River solid content that coal slurry gasifier generates is big (about 3-8wt.%), to pipeline and valve blockage, serious wear,
It influences Heisui River system and device to operate normally, maintenance of stopping in emergency is caused when serious, causes serious hidden danger to equipment safety operation；
And gasification ash water is recycled after multistage flash distillation and flocculation sedimentation are removed admittedly, so that the grey water hardness is higher and higher, causes to flash
The blocking of the equipment scalings such as tank, oxygen-eliminating device, causes to seriously affect to device stable operation.
Coal water slurry gasifying device operates normally, and coal quality and water quality are two technic indexs of strict control, water quality be with
The variation of coal quality and the changes in process parameters of gasifier operation and fluctuate.PH, basicity, hardness number are with buck in buck water quality
Fouling have a direct relationship, the CaCO that fouling generates3Equal salts in buck colloid and suspended particle deposit, be adsorbed in
In equipment and ash-water pipeline inner wall, and the difference of the thermal expansion coefficient of layer of scale and pipeline, gasifier operation condition change with
And layer of scale can crack loosely when stopping vehicle, block pipeline and valve so as to cause falling off for layer of scale.Also, high concentration Cl-
Stronger stress corrosion will be generated to pipeline and equipment especially stainless steel material under high-temperature and high-pressure conditions.
Washing at present in typical coal-water slurry gasification, after the washed tower washing of the crude synthesis gas that gasification furnace is generated
What water and gasification furnace generated contains after solid cold shocking water is sent to high pressure flash, low pressure flash, vacuum flashing into subsider, through flocculating
Supernatant liquor is discharged into ash water tank after precipitating, and buck enters scrubbing tower as synthesis gas washing water after pump is promoted to deoxidation heating and follows
Ring uses.The process needs outlet major part buck decontamination water treatment station, and accounting is entire coal chemical industry water treatment station water
50% or so, while requiring supplementation with desalted water to keep ash water system to balance, this water is generally the 20- of the total grey water of system
30% or so.
Summary of the invention
The purpose of the invention is to the Heisui River reuse degree for overcoming existing coal gasification course to generate not high and easy fouling,
The defect of blocking and etching system provides the reuse degree and reduction knot in a kind of Heisui River that can be improved coal gasification course generation
The processing method and gasification of coal and its system in the Heisui River that the coal gasification of dirt, blocking and etching system risk generates.
To achieve the goals above, one aspect of the present invention provides a kind of processing method in Heisui River that coal gasification generates, the party
Method includes:
(1) Heisui River is subjected to high pressure flash, and the Heisui River after high pressure flash is subjected to eddy flow except solid processing；
(2) resulting top clear stream successively carries out low pressure flash and vacuum flashing after the eddy flow being removed solid processing；
(3) by after the vacuum flashing Heisui River and the eddy flow except after solid processing resulting bottom concentrated water carry out at sedimentation
Reason；
(4) supernatant obtained by the settlement treatment and calcium hydroxide and sodium carbonate are subjected to haptoreaction；
(5) in the presence of flocculant, the Heisui River after the haptoreaction is subjected to flocculation treatment；
(6) Heisui River after the flocculation treatment is settled, will sedimentation gained supernatant successively be filtered processing and
Electrodialysis process.
Second aspect of the present invention provides a kind of gasification of coal, this method comprises:
(a) coal is sent into gasification furnace and is gasified, obtain crude synthesis gas and containing solid cold shocking water；
(b) the resulting crude synthesis gas of step (a) is sent into scrubbing tower and is washed, obtain net synthesis gas and washing water；
(c) it is sent step (a) is resulting as Heisui River to high pressure containing solid cold shocking water and the resulting portion of washing water of step (b)
High pressure flash is carried out in flash column, and the Heisui River after high pressure flash is sent to cyclone separator and carries out eddy flow except solid processing；
(d) resulting top clear stream is successively sent into Low Pressure Flashing Column and vacuum flasher after the eddy flow being removed solid processing
Low pressure flash and vacuum flashing are carried out respectively；
(e) by after the vacuum flashing Heisui River and the eddy flow except after solid processing resulting bottom concentrated water send to subsider
Middle carry out settlement treatment；
(f) calcium hydroxide and sodium carbonate is sent into reaction tank to carry out haptoreaction supernatant obtained by the settlement treatment；
(g) Heisui River after the haptoreaction is sent into flocculation basin, flocculation treatment is carried out in the presence of flocculant；
(h) Heisui River after the flocculation treatment is sent and is settled into sedimentation basin, sedimentation gained supernatant is successively sent
It is filtered processing and electrodialysis process respectively into filter and electrodialysis reactor.
Third aspect present invention provides a kind of coal gasification system, which includes:
Gasification furnace, for coal to gasify, to obtain crude synthesis gas and containing solid chilled water；
Scrubbing tower obtains net synthesis gas and washing water for washing the resulting crude synthesis gas of gasification furnace；
High pressure flash tower, for carrying out high pressure flash to the Heisui River being used as containing solid cold shocking water and partial washing water；
Cyclone separator, for carrying out eddy flow except solid processing to the Heisui River after the high pressure flash；
Sequentially connected Low Pressure Flashing Column and vacuum flasher are clear for resulting top after removing solid processing to the eddy flow
Stream successively carries out low pressure flash and vacuum flashing；
Subsider, for by after the vacuum flashing Heisui River and the eddy flow except after solid processing resulting bottom concentrated water into
Row settlement treatment；
Reaction tank, for supernatant obtained by the settlement treatment and calcium hydroxide and sodium carbonate to be carried out haptoreaction；
Flocculation basin, for the Heisui River after the haptoreaction to be carried out flocculation treatment in the presence of flocculant；
Sedimentation basin, for settling the Heisui River after the flocculation treatment；
Sequentially connected filter and electrodialysis reactor, for will settle gained supernatant successively be filtered processing and
Electrodialysis process.
By using the processing method in the Heisui River that coal gasification of the invention generates, the hardness in Heisui River can be greatly reduced,
Corrosive salt is effectively removed, the especially processing method in the Heisui River for generating the coal gasification is used in coal gasification technique
When, it can realize and coal gasification is generated in the case where not influencing original technique and system layout and only increasing part processing equipment
Heisui River processing, the problem of not only having can solve fouling, blocking caused by buck and etching system, but also the recycling of water can be improved
Rate reduces the outer discharge capacity of buck.
Detailed description of the invention
Fig. 1 is a kind of coal gasification system of embodiment according to the present invention.；
Fig. 2 is a kind of partial schematic diagram of the coal gasification system of embodiment according to the present invention.
Description of symbols
1: gasification furnace；2: cyclone separator；3: high pressure flash tower；4: Low Pressure Flashing Column；5: vacuum flasher；6: sedimentation
Slot；7: reaction tank；8: flocculation basin；9: sedimentation basin；10: filter；11: electrodialysis reactor；12: ash water tank；13: dosing dress
It sets；14: oxygen-eliminating device；15: scrubbing tower；16: Venturi scrubber；17: dreg-locking hopper；18: dragveyer；19: slag breaker.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
First aspect present invention provides a kind of processing method in Heisui River that coal gasification generates, this method comprises:
(1) Heisui River is subjected to high pressure flash, and the Heisui River after high pressure flash is subjected to eddy flow except solid processing；
(2) resulting top clear stream successively carries out low pressure flash and vacuum flashing after the eddy flow being removed solid processing；
(3) by after the vacuum flashing Heisui River and the eddy flow except after solid processing resulting bottom concentrated water carry out at sedimentation
Reason；
(4) supernatant obtained by the settlement treatment and calcium hydroxide and sodium carbonate are subjected to haptoreaction；
(5) in the presence of flocculant, the Heisui River after the haptoreaction is subjected to flocculation treatment；
(6) Heisui River after the flocculation treatment is settled, will sedimentation gained supernatant successively be filtered processing and
Electrodialysis process.
According to the present invention, what the Heisui River that the coal gasification generates typically referred to come out after gasification furnace contains solid cold shocking water
And/or it from the portion of washing water washed after crude synthesis gas flowed out in scrubbing tower, usually needs to handle in coal gasification course
Heisui River be to refer to that is come out after gasification furnace washes containing the part washed after crude synthesis gas flowed out in solid cold shocking water and scrubbing tower
Wash the mixture of water.Generally, the washing water quality situation washed after crude synthesis gas flowed out in scrubbing tower is better than containing solid
Cold shocking water, therefore, it is generally the case that another part washing water washed after crude synthesis gas that will also be flowed out in portion washes tower
It is back in gasification furnace as cold shocking water.Wherein, it is described refer to that cold shocking water and water-coal-slurry are gasified containing solid cold shocking water after, outflow
Contain a large amount of solid matters and other impurity, have compared with high pollution waste water.
According to the present invention, it is generally the case that the solid content in the Heisui River that the coal gasification generates is that 0.5-8 weight %, pH are
6-10, Ca2+Content is 150-600mg/L, Mg2+Content is 8-20mg/L, Cl-Content is 90-300mg/L, SS 80-500mg/
L, COD 150-1000mg/L, conductivity are 2000-7000 μ s/cm.
According to the present invention, Heisui River is successively usually subjected to high pressure flash, low pressure flash and vacuum flashing, and side of the invention
Method first carries out eddy flow except solid processing after above-mentioned Heisui River to be carried out to high pressure flash, then successively carries out low pressure flash and vacuum flashing,
It is possible thereby to remove most of solid particle in Heisui River, before low pressure flash and vacuum flashing to reduce system congestion risk.
Under preferable case, in step (1), the eddy flow except solid processing so that the solid content in the Heisui River after high pressure flash reduce by 60% with
On.The eddy flow can be carried out except solid processing using the cyclone separator of this field routine, and thus the top clear liquid of eddy flow out into
The next flash distillation link of row, bottom concentrated water are then sent to progress settlement treatment.
According to the present invention, the present invention does not limit the high pressure flash, low pressure flash and vacuum flashing particularly, can adopt
It is carried out with the operation of this field routine, such as shown in Figure 1, in high pressure flash tower 3, Low Pressure Flashing Column 4 and vacuum flasher 5
The high pressure flash, the low pressure flash and the vacuum flashing are carried out respectively.Wherein, the high pressure flash, low pressure flash and
Processing pressure used by vacuum flashing is different, and the condition of the high pressure flash for example may include: that temperature is 160-200 DEG C,
Gauge pressure is 5-15MPa；The condition of low pressure flash for example may include: that temperature is 110-140 DEG C, gauge pressure 0.2-1MPa；Vacuum
The condition of flash distillation for example may include: that temperature is 30-60 DEG C, and gauge pressure is 0.05MPa or less.
According to the present invention, in step (3) by after the vacuum flashing Heisui River and the eddy flow except resulting after solid processing
Bottom concentrated water carries out settlement treatment, the solid particulate matter in Heisui River can settle down, gained supernatant carries out subsequent again
Processing, the condition of the sedimentation include: that temperature is 10-50 DEG C, residence time 30-90min.
According to the present invention, the mode cooperated by using calcium hydroxide and sodium carbonate, can preferably reduce the hard of Heisui River
Degree, the reaction equation of foundation are for example listed below:
Temporary hardness is removed, Ca is made2+And Mg2+Form precipitating:
Ca(HCO3)2+Na2CO3=CaCO3↓+2NaHCO3
Mg(HCO3)2+Na2CO3=MgCO3↓+2NaHCO3
In higher ph, MgCO3It hydrolyzes quickly:
MgCO3+H2O→Mg(OH)2↓+CO2↑
Remove non-carbonate hardness:
CaSO4+Na2CO3→CaCO3↓+Na2SO4
CaCl2+Na2CO3→CaCO3↓+2NaCl
MgSO4+Na2CO3→MgCO3+Na2SO4
MgCl2+Na2CO3→MgCO3+2NaCl
As it can be seen that high ph-values environment and C that calcium hydroxide providesa2+Ionic environment can assist sodium carbonate efficiently to reduce Heisui River
Hardness.
In order to fully reduce hardness again will not overdose, under preferable case, in step (4), relative to 1t's
Supernatant obtained by the settlement treatment, the dosage of calcium hydroxide are 0.08-0.15kg, and the dosage of sodium carbonate is 1.3-1.4kg.It should
Obtained by calcium hydroxide can be and react as lime with water, the calcium hydroxide be can be with the concentration of 5-10 weight % as a result,
Aqueous solution provides.Sodium carbonate can be provided with the aqueous solution of the concentration of 5-15 weight %.It should be understood that working as above-mentioned coal gasification
When the processing method in the Heisui River of generation is continuous processing method, in step (4), after the vacuum flashing of 1t/h
Heisui River, the dosage of calcium hydroxide are preferably 0.08-0.15kg/h, and the dosage of sodium carbonate is 1.3-1.4kg/h.
In the case of, according to the invention it is preferred to, in step (4), the catalytic condition includes: that temperature is 10-50 DEG C,
Time is 30-90min.It should be understood that when the processing method in the Heisui River of above-mentioned coal gasification generation is continuous processing method
When, which is the residence time.
According to the present invention, in step (5), in the presence of flocculant, the Heisui River after the haptoreaction is carried out at flocculation
Reason, can further remove the colloid and precipitating in Heisui River.The flocculant can use the various flocculations of this field routine
Agent, for example, one of inorganic flocculating agent and organic flocculant or a variety of, wherein the inorganic flocculating agent for example can be poly-
Close one of aluminium chloride (PAC), polyaluminium sulfate (PAS), bodied ferric sulfate (PFS), poly-ferric chloride (PFC) etc. or more
Kind, the organic flocculant for example can be in polyacrylamide, Sodium Polyacrylate, polyvinyl pyridine salt, polyethyleneimine etc.
It is one or more.Preferably, relative to the Heisui River after the haptoreaction of 1t, the dosage of the flocculant is 0.15-
0.2kg (in terms of dry weight).The flocculant provides preferably in the form of its aqueous solution, such as the flocculant is 0.1-0.3 weight
Measure the aqueous solution of %.It should be understood that when the processing method in the Heisui River that above-mentioned coal gasification generates is continuous processing method,
In step (3), relative to the Heisui River after the haptoreaction of 1t/h, the dosage of the flocculant is preferably 0.15-0.2kg/
h。
In the case of, according to the invention it is preferred to, the condition of the flocculation treatment includes: that temperature is 10-50 DEG C, time 30-
60min.It should be understood that when the processing method in the Heisui River that above-mentioned coal gasification generates is continuous processing method, the flocculation
The time of processing is the residence time.
According to the present invention, in step (6), the Heisui River after the flocculation treatment is settled, by sedimentation gained supernatant
Successively it is filtered processing and electrodialysis process, wherein treated Heisui River can be stood by sedimentation, so that precipitating is poly-
Collect and deposit to bottom, upper clear supernate is then sent to the processing of lower step；By filtration treatment, the suspended matter in water can be further removed
And colloid；Electrodialysis process can remove effectively the salt in water, such as removal Ca2+、Mg2+、Na+、Cl-Plasma.
In the case of, according to the invention it is preferred to, in step (6), the condition of sedimentation includes: that temperature is 10-40 DEG C, and the time is
30-90min.Under preferable case, the condition of the filtration treatment includes: that temperature is 10-40 DEG C, time 10-30min.It is preferred that
In the case of, the condition of the electrodialysis process includes: that pH value is 6-6.5, and temperature is 10-40 DEG C, time 10-30min.It should
Understand, when the processing method in the Heisui River that above-mentioned coal gasification generates is continuous processing method, which all refers to stop
Time.
According to the present invention, the filtration treatment include sand filtration and security personnel filtering, also i.e. by the upper clear supernate of above-mentioned sedimentation according to
It is secondary to be filtered by sand filtration and security personnel, entering electrodialysis process.
According to the present invention, it send by Heisui River to be processed to before electrodialysis process, first by the Heisui River to be processed and acid
It is mixed, the pH of the water to be processed is adjusted to 6-6.5 to reach.Here acid for example can be HCl and/or H2SO4。
According to the present invention, although there is no particular limitation by the present invention, the processing side in the Heisui River that above-mentioned coal gasification generates
Method can carry out in set of system.In a preferred embodiment of the invention, as illustrated in fig. 1 and 2, the present invention
A kind of processing method in Heisui River that coal gasification generates is provided, this method comprises:
(1) Heisui River is sent and carries out high pressure flash into high pressure flash column 3, and the Heisui River after high pressure flash is sent to eddy flow point
It is handled from eddy flow is carried out in device 2 except solid；
(2) resulting top clear stream is sent to Low Pressure Flashing Column 4 and vacuum flasher 5 successively after the eddy flow being removed solid processing
Carry out low pressure flash and vacuum flashing；
(3) by after the vacuum flashing Heisui River and the eddy flow except after solid processing resulting bottom concentrated water send to subsider
Settlement treatment is carried out in 6；
(4) supernatant obtained by the settlement treatment is sent into reaction tank 7 and contact instead with calcium hydroxide and sodium carbonate
It answers；
(5) Heisui River after the haptoreaction is sent into flocculation basin 8, flocculation treatment is carried out in the presence of flocculant；
(6) Heisui River after the flocculation treatment is sent into sedimentation basin 9 and is settled, sedimentation gained supernatant is successively sent
Processing and electrodialysis process are successively filtered into filter 10 and electrodialysis reactor 11.The device that the above method is related to is equal
For the conventional equipment of this field, details are not described herein.
As illustrated in fig. 1 and 2, the present invention provides a kind of gasification of coal, this method comprises:
(a) coal is sent into gasification furnace 1 and is gasified, obtain crude synthesis gas and containing solid cold shocking water；
(b) the resulting crude synthesis gas of step (a) is sent into scrubbing tower 15 and is washed, obtain net synthesis gas and washing
Water；
(c) it is sent step (a) is resulting as Heisui River to high pressure containing solid cold shocking water and the resulting portion of washing water of step (b)
High pressure flash is carried out in flash column 3, and the Heisui River after high pressure flash is sent to cyclone separator 2 and carries out eddy flow except solid processing；
(d) resulting top clear stream is successively sent to Low Pressure Flashing Column 4 and vacuum flasher 5 after the eddy flow being removed solid processing
It is middle to carry out low pressure flash and vacuum flashing respectively；
(e) by after the vacuum flashing Heisui River and the eddy flow except after solid processing resulting bottom concentrated water send to subsider
(6) settlement treatment is carried out in；
(f) calcium hydroxide and sodium carbonate is sent into reaction tank 7 to carry out haptoreaction supernatant obtained by the settlement treatment；
(g) Heisui River after the haptoreaction is sent into flocculation basin 8, flocculation treatment is carried out in the presence of flocculant；
(h) Heisui River after the flocculation treatment is sent into sedimentation basin 9 and is settled, sedimentation gained supernatant is successively sent
It is filtered processing and electrodialysis process respectively into filter 10 and electrodialysis reactor 11.
According to the present invention, in step (a), the coal can be fed through in gasification furnace 1 in the form of water-coal-slurry, the water coal
Slurry be coal content in the mixture of the coal containing a large amount of coal and water, such as the water-coal-slurry be 55-70 weight % (preferably
60-70 weight %).Or the coal can also be fed through in gasification furnace 1 in the form of dry pulverized coal by carrier gas (such as nitrogen), more
It is preferred that the coal is fed through in gasification furnace 1 in the form of water-coal-slurry.Special limit is had no to the coal gasification condition in step (a)
It is fixed, the coal gasification condition of this field routine can be used, it is preferable that in step (a), the condition of the gasification in gasification furnace 1
It include: pressure for 2-9MPa, temperature is 1200-1400 DEG C.It is highly preferred that in step (a), the item of the gasification in gasification furnace 1
Part includes: that pressure is 2.5-8MPa (gauge pressure), and temperature is 1200-1350 DEG C.It, will by the coal gasification process of step (a)
The crude synthesis gas of the carbon dioxide containing certain solid suspension and certain content is obtained, and there is higher solids content, higher
Hardness etc. contains solid cold shocking water, and the water quality situation for containing solid cold shocking water is as described above.
According to the present invention, the slag charge of above-mentioned 1 lower end of gasification furnace discharge, can be by being arranged in the break of 1 lower end of gasification furnace
Machine 19 carries out after being crushed, and send into dreg-locking hopper 17, to mix with part water, (water here be can be after electrodialysis process
Water), gained mixture fishes out back solid slag through dragveyer 18, remaining Heisui River part sent again into vacuum flasher 5 with from low
The water of pressure flash column 4 is flashed together, and is then further processed, as shown in Figure 1.
According to the present invention, in step (b), the resulting crude synthesis gas of step (a) is sent into scrubbing tower 15 and is carried out by step (b)
Washing, main purpose are to remove the solid suspension contained in crude synthesis gas, just contain one in washing water resulting in this way
The water quality situation of fixed solid suspension, the washing water is as described above.It, can be with before entering scrubbing tower 15 and washing
It is washed so that crude synthesis gas is introduced into Venturi scrubber 16, which can washing using part
Wash water of the washing water of tower 15 as washing crude synthesis gas.
According to the present invention, in step (c), step (a) is resulting containing solid cold shocking water and the resulting portion washes of step (b)
Water is first sent as Heisui River carries out high pressure flash into high pressure flash column (3), then the Heisui River after high pressure flash is sent to cyclonic separation
Device (2) carries out eddy flow except solid processing, can remove most solid particle in Heisui River, reduces system congestion risk.It is preferred that feelings
Under condition, the eddy flow is except solid processing so that the solid content in the Heisui River after high pressure flash reduces by 60% or more.The eddy flow is except solid processing
As described above, details are not described herein.
According to the present invention, high pressure flash, low pressure flash and vacuum flashing are as described above, and which is not described herein again.Such as Fig. 1 institute
Show, wherein the steam generated after high pressure flash and low pressure flash can be used in degasifier 14 providing heat with to electrodialysis
Water after reason carries out deoxidation treatment.And the steam that vacuum flashing generates can enter additional methanol synthesis unit (not shown) and use
The synthesizing methanol after purified treatment.
According to the present invention, in step (e), by after the vacuum flashing Heisui River and the eddy flow except resulting after solid processing
Bottom concentrated water, which is sent, carries out settlement treatment into subsider 6, and the settlement treatment is as described above, and details are not described herein.
According to the present invention, in step (f), by supernatant obtained by the settlement treatment send into reaction tank 7 calcium hydroxide and
Sodium carbonate carries out haptoreaction；The haptoreaction is as described above, and details are not described herein.Wherein, as illustrated in fig. 1 and 2,
Calcium hydroxide and sodium carbonate can be provided by chemicals dosing plant 13.
According to the present invention, in step (g), the Heisui River after the haptoreaction is sent into flocculation basin 8, is existed in flocculant
Lower carry out flocculation treatment；The flocculation treatment is as described above, and details are not described herein.Wherein, as illustrated in fig. 1 and 2, flocculation
Agent can be provided by the chemicals dosing plant 13 of flocculant.
According to the present invention, in step (h), the Heisui River after the flocculation treatment is sent into sedimentation basin 9 and is settled, will sunk
Drop gained supernatant is successively sent is filtered processing and electrodialysis process into filter 10 and electrodialysis reactor 11 respectively；Its
In, sedimentation, filtration treatment and electrodialysis process are as introduced above, and details are not described herein.
According to the present invention it is possible to the resulting water of electrodialysis process is stored in ash water tank 12, temporarily to store and collect
Method of the invention handles resulting water.And progress others can be discharged further in the water a part stored in the ash water tank 12
Sewage treatment (water of the part can be only 50 weight % hereinafter, it is preferred that 40 weight % or less), another part can then follow
Loopback is with (water of the part is 50 weight % or more, preferably 60 weight % or more), as being previously mentioned in following steps (i)
's.
According to the present invention, as described above, the method for the invention Heisui River major part circulating and recovering that can make that treated,
For this purpose, this method further include: step (i) send the part water after the electrodialysis process into scrubbing tower 15 and/or gasification furnace 1
(as described above, the water of the part is 50 weight % or more, preferably 60 weight % or more) is recycled.In step (i),
In order to be conducive to the production and washing of crude synthesis gas, before being recycled, it is also necessary to by the part after the reverse osmosis treatment
Water carries out deoxidation treatment, as a result, as shown in Figure 1, before this method can also include: step (i), by using the height
Pressure flash distillation and/or the resulting steam of low pressure flash carry out the part water after the reverse osmosis treatment at deoxygenation in oxygen-eliminating device 14
Reason.As described above, deoxygenation will be carried out in oxygen-eliminating device 14 treated that water send that crude synthesis gas is washed into scrubbing tower, obtain
Washing water, it is good that the water quality situation ratio of the washing water contains solid cold shocking water, therefore the washing water of part can be sent as cold shocking water
Enter into gasification furnace 1, it is therefore preferred that the mode of the recycling of the part water after the electrodialysis process are as follows: by adopting
With the high pressure flash and/or the resulting steam of low pressure flash by the part water after the electrodialysis process in oxygen-eliminating device 14 into
Then row deoxygenation processing will carry out deoxygenation in oxygen-eliminating device 14 treated water and send to wash crude synthesis gas into scrubbing tower 15, obtain
To washing water, portion of washing water is sent into gasification furnace 1 and is reacted as cold shocking water with coal, obtains crude synthesis gas and containing solid cold shock
Water, so that above-mentioned coal gasification process is recycled for another example.
As depicted in figs. 1 and 2, the present invention also provides a kind of coal gasification system, which includes:
Gasification furnace 1, for coal to gasify, to obtain crude synthesis gas and containing solid chilled water；
Scrubbing tower 15 obtains net synthesis gas and washing water for washing the resulting crude synthesis gas of gasification furnace 1；
High pressure flash tower 3, for carrying out high pressure flash to the Heisui River being used as containing solid cold shocking water and partial washing water；
Cyclone separator 2, for carrying out eddy flow except solid processing to the Heisui River after the high pressure flash；
Sequentially connected Low Pressure Flashing Column 4 and vacuum flasher 5 are used for the eddy flow except resulting top after solid processing
Clear stream successively carries out low pressure flash and vacuum flashing；
Subsider 6, for by after the vacuum flashing Heisui River and the eddy flow except resulting bottom concentrated water after solid processing
Carry out settlement treatment；
Reaction tank 7, for supernatant obtained by the settlement treatment and calcium hydroxide and sodium carbonate to be carried out haptoreaction；
Flocculation basin 8, for the Heisui River after the haptoreaction to be carried out flocculation treatment in the presence of flocculant；
Sedimentation basin 9, for settling the Heisui River after the flocculation treatment；
Sequentially connected filter 10 and electrodialysis reactor 11 are successively filtered place for that will settle gained supernatant
Reason and electrodialysis process.
According to the present invention, the coal gasification system is that a set of usage on black water is increased in existing gasification system
Device, the addition of the device of the set usage on black water realize the processing in the Heisui River generated to coal gasification, both can solve buck and made
At fouling, blocking and the problem of etching system, and the rate of recovery of water can be improved, reduces the outer discharge capacity of buck, and will not shadow
Ring original technique and device layout.
The coal gasification system can also include: chemicals dosing plant 13.Wherein, as shown in Fig. 2, the chemicals dosing plant 13 includes
The chemicals dosing plant 13 (providing calcium hydroxide and sodium carbonate for above-mentioned reaction tank 7) of calcium hydroxide and sodium carbonate is provided, flocculation is provided
The chemicals dosing plant 13 (providing flocculant for above-mentioned flocculation basin 8) of agent and the chemicals dosing plant for providing acid (are not shown, for after filtration treatment
Buck provide acid, with enter electrodialysis reactor before reduce pH).
The system can also include: oxygen-eliminating device 14, for resulting by using the high pressure flash and/or low pressure flash
Part water after the reverse osmosis treatment is carried out deoxygenation processing by steam.
The system can also include: that ash water tank 12 (may refer to for storing buck after electrodialysis reactor 11 is handled
Description in text).
The system can also include: dreg-locking hopper 17, dragveyer 18 and slag breaker 19, the slag that above-mentioned 1 lower end of gasification furnace comes out
Material can be carried out after being crushed by the way that the slag breaker 19 of 1 lower end of gasification furnace is arranged in, be sent into dreg-locking hopper 17, with mixed with part water
It closes (water here can be the water after electrodialysis process), gained mixture fishes out back solid slag through dragveyer 18, remaining
Heisui River part is sent again to be flashed together with the water from Low Pressure Flashing Column 4 into vacuum flasher 5, and is then carried out in next step
Processing (as described above).
By using the processing method in the Heisui River that coal gasification of the invention generates, the hardness in Heisui River can be greatly reduced,
Corrosive salt is effectively removed, the especially processing method in the Heisui River for generating the coal gasification is used in coal gasification technique
When, can not influence original technique and device layout only increase part processing equipment in the case where, realize to coal gasification generate
Heisui River processing, the problem of not only having can solve fouling, blocking caused by buck and etching system, but also the recycling of water can be improved
Rate reduces the outer discharge capacity of buck.Wherein, the outer discharge capacity of buck can reduce 60 weight % or more, and the supply of fresh water can reduce 100 every year
Ten thousand tons, water resource has been saved, has reduced water pollution, and has also reduced investment and operation ingredient.
The present invention will be described in detail by way of examples below.
In following embodiment, using coal gasification system shown in FIG. 1 carry out, specifically, the system include: gasification furnace 1,
Cyclone separator 2, high pressure flash tower 3, Low Pressure Flashing Column 4, vacuum flasher 5, subsider 6, reaction tank 7, flocculation basin 8, precipitating
Pond 9, filter 10, electrodialysis reactor 11, ash water tank 12, chemicals dosing plant 13, oxygen-eliminating device 14, scrubbing tower 15, Venturi scrubbing
Device 16, dreg-locking hopper 17, dragveyer 18 and slag breaker 19；Wherein, made in gasification furnace 1 using the portion of washing water from scrubbing tower 15
It is reacted for cold shocking water with coal, obtains crude synthesis gas and containing solid cold shocking water；Crude synthesis gas successively send to Venturi scrubber 16 and washes
It washs and is washed (slurry is the buck after deoxidation treatment after reverse osmosis treatment in scrubbing tower 15) in tower 15, obtain net
Synthesis gas (not shown) and washing water；It send another part washing water and containing solid cold shocking water and carries out high pressure into high pressure flash column 3
It flashes, the Heisui River after high pressure flash, which is sent into cyclone separator 2, carries out eddy flow except solid processing, which flows out
Top clear stream successively send into Low Pressure Flashing Column 4 and vacuum flasher 5 and successively carry out low pressure flash and vacuum flashing, high pressure is dodged
Steaming the steam that tower 3 and Low Pressure Flashing Column 4 generate send into oxygen-eliminating device 14 water for heating electrodialysis process to carry out deoxidation treatment；
By after the vacuum flashing Heisui River and 2 bottom concentrated water of cyclone separator send into subsider 6 and settle；By the supernatant of sedimentation
Liquid, which is sent into reaction tank 7, carries out haptoreaction with calcium hydroxide and sodium carbonate, and the calcium hydroxide and sodium carbonate are by offer hydroxide
The chemicals dosing plant 13 of calcium and sodium carbonate provides；Heisui River after the haptoreaction is sent into flocculation basin 8, in the presence of flocculant
Flocculation treatment is carried out, which is provided by the chemicals dosing plant 13 of offer flocculant；By the Heisui River after the flocculation treatment send to
Settled in sedimentation basin 9, will sedimentation gained supernatant successively send to filter 10 (successively carry out sand filtration and security personnel filtering) and
Processing and electrodialysis process are filtered in electrodialysis reactor 11 respectively, wherein before entering in electrodialysis reactor 11
First adopt the pH for being adjusted with acid drainage；The water that electrodialysis reactor 11 comes out is sent into ash water tank 12 and is stored, gained buck portion
It exceptionally arranges, partially send and as above handled into oxygen-eliminating device 14, so recycle.
Wherein, the calcium hydroxide in the chemicals dosing plant 13 of calcium hydroxide is obtained by lime and water hybrid reaction, concentration
For 10 weight %.In the chemicals dosing plant 13 of sodium carbonate, the concentration of aqueous sodium carbonate is 12 weight %.
The flocculant provided in the chemicals dosing plant 13 of flocculant is available from Tianjin chemical research institute TS-C polyacrylamide,
Concentration is 0.2 weight %.
There is provided the acid in the chemicals dosing plant of acid is hydrochloric acid, and the concentration of aqueous hydrochloric acid solution is 30 weight %.
Embodiment 1
The processing method and gasification of coal in the Heisui River that the present embodiment is used to illustrate that coal gasification of the invention generates and its
System.
It is carried out using gasification system shown in FIG. 1, process is as shown above:
Wherein, the coal being sent into gasification furnace 1 is the water-coal-slurry of 60 weight % of coal-water fluid concentration, gasification condition are as follows: pressure is
1250 DEG C of 6.35MPa, temperature；
The Heisui River solid content that high pressure flash tower 3 comes out is 7.3 weight %, and the solid content being discharged at the top of cyclone separator 2 is
4.1 weight %；The water of the supernatant W1 of subsider 6, the supernatant W2 of sedimentation basin 9, the water W3 come out in electrodialysis reactor 12
Matter situation is as shown in table 1；
Send the flow to the Heisui River of high pressure flash column 3 be 200t/h (volume ratio containing solid chilled water and washing water be 1:
0.1) it is 180 DEG C that, the condition of high pressure flash, which includes: temperature, gauge pressure 10MPa；
Sending the flow to the Heisui River of cyclone separator 2 is 177t/h；
Sending the flow to the Heisui River of Low Pressure Flashing Column 4 is 124t/h；The condition of low pressure flash includes: that temperature is 130 DEG C, table
Pressure is 0.27MPa；
Sending the flow to the Heisui River of vacuum flasher 5 is 108t/h, and the condition of vacuum flashing includes: that temperature is 45 DEG C, table
Pressure is 0.01MPa；
Sending the flow to the Heisui River of subsider 6 is that 145t/h (from treated the Heisui River of vacuum flasher 5 and carrys out spin current
The weight ratio of separator 2 is 1:0.58), the condition of the sedimentation includes: that temperature is 40 DEG C, residence time 50min；
Send to the Heisui River of reaction tank 7 flow be 125t/h, calcium hydroxide aqueous solution add flow be 12.5kg/h (with
The poidometer of calcium hydroxide), the flow that adds of aqueous sodium carbonate is 171.9kg/h (with the poidometer of sodium carbonate), reaction tank
The catalytic condition of middle progress includes: that temperature is 40 DEG C, residence time 40min；
Sending the flow to the Heisui River of flocculation basin 8 is 125t/h, and the flow that adds of flocculant aqueous solution is 22.5kg/h (with wadding
Solidifying agent dry weight meter), it is 20 DEG C that the condition of the flocculation treatment carried out in flocculation basin, which includes: temperature, residence time 40min；
Sending the flow to the Heisui River of sedimentation basin 9 is 115t/h, and the condition of sedimentation includes: that temperature is 20 DEG C, and the residence time is
50min；
Sending the flow to the Heisui River of filter 10 is 115t/h, and the condition of filtration treatment includes: that temperature is 20 DEG C, when stop
Between be 15min；
Heisui River pH to about 6 is adjusted before sending to electrodialysis reactor 11, is then that 115t/h is sent to electrodialysis reaction with flow
Electrodialysis process is carried out in device 11, the condition of electrodialysis process includes: that temperature is 20 DEG C, residence time 15min.
Wherein, the water come out after electrodialysis process is after ash water tank 12, and the grey water flow of outlet is 34t/h, circulation
Grey water flow is 81t/h.So circulation for 24 hours after, outer displacement is only 1944t, and system without fouling, without blocking, corrosion-free.
Table 1
Comparative example 1
System according to figure 1 carries out coal gasification, unlike, which does not include reaction tank 6, flocculation basin 8, sinks
Shallow lake pond 9, filter 10, electrodialysis reactor 11, but directly by treated in vacuum flasher 5, water is sent into settling tank 6
It being settled, and supernatant liquor is sent into ash water tank 12, the water quality situation of the water W3 in the ash water tank 12 is as shown in table 2 below,
To which the grey water flow of outlet is 135t/h, the grey water flow of circulation is 30t/h.After so recycling for 24 hours, outer displacement is
3240t, and system has a large amount of fouling, and part has corrosion phenomenon.
Table 2
It can be seen that this black water treatment system by the comparison of embodiment 1 and comparative example 1 and be able to solve gasification system knot
The problem of dirt, burn into blocking, grey black reusing rate is improved, outer displacement is reduced.
By compare above as can be seen that usage on black water method and system of the invention be able to solve gasification system fouling,
The problem of burn into blocks improves usage on black water effect and grey black reusing rate, reduces outer displacement.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (17)
1. a kind of processing method in the Heisui River that coal gasification generates, which is characterized in that this method comprises:
(1) Heisui River is subjected to high pressure flash, and the Heisui River after high pressure flash is subjected to eddy flow except solid processing；
(2) resulting top clear stream successively carries out low pressure flash and vacuum flashing after the eddy flow being removed solid processing；
(3) by after the vacuum flashing Heisui River and the eddy flow except after solid processing resulting bottom concentrated water carry out settlement treatment；
(4) supernatant obtained by the settlement treatment and calcium hydroxide and sodium carbonate are subjected to haptoreaction；
(5) in the presence of flocculant, the Heisui River after the haptoreaction is subjected to flocculation treatment；
(6) Heisui River after the flocculation treatment is settled, sedimentation gained supernatant is successively filtered processing and electric osmose
Analysis processing.
2. according to the method described in claim 1, wherein, in step (1), the eddy flow is except solid processing is so that after high pressure flash
The solid content in Heisui River reduces by 60% or more.
3. method according to claim 1 or 2, wherein in step (4), relative on the settlement treatment gained of 1t
Clear liquid, the dosage of calcium hydroxide are 0.08-0.15kg, and the dosage of sodium carbonate is 1.3-1.4kg；
Preferably, it is 10-50 DEG C that the catalytic condition, which includes: temperature, time 30-90min.
4. method described in any one of -3 according to claim 1, wherein in step (5), the flocculant is inorganic flocculation
One of agent and organic flocculant are a variety of；
Preferably, the inorganic flocculating agent is one in aluminium polychloride, polyaluminium sulfate, bodied ferric sulfate and poly-ferric chloride
Kind is a variety of；The organic flocculant is one in polyacrylamide, Sodium Polyacrylate, polyvinyl pyridine salt and polyethyleneimine
Kind is a variety of；
Preferably, relative to the Heisui River after the haptoreaction of 1t, the dosage of the flocculant is 0.15-0.2kg；
Preferably, it is 10-50 DEG C that the condition of the flocculation treatment, which includes: temperature, time 30-60min.
5. method described in any one of -4 according to claim 1, wherein in step (6), the condition of the sedimentation includes:
Temperature is 10-50 DEG C, time 30-90min；
Preferably, it is 10-40 DEG C that the condition of the filtration treatment, which includes: temperature, time 10-30min；
Preferably, it is 6-6.5 that the condition of the electrodialysis process, which includes: pH value, and temperature is 10-40 DEG C, time 10-30min.
6. method described in any one of -5 according to claim 1, wherein the solid content in the Heisui River that the coal gasification generates is
0.5-8 weight %, pH 6-10, Ca2+Content is 150-600mg/L, Mg2+Content is 8-20mg/L, Cl-Content is 90-
300mg/L, SS 80-500mg/L, COD 150-1000mg/L, conductivity are 2000-7000 μ s/cm.
7. a kind of gasification of coal, which is characterized in that this method comprises:
(a) coal is sent into gasification furnace (1) and is gasified, obtain crude synthesis gas and containing solid cold shocking water；
(b) the resulting crude synthesis gas of step (a) is sent into scrubbing tower (15) and is washed, obtain net synthesis gas and washing water；
(c) it is sent step (a) is resulting as Heisui River to high pressure flash containing solid cold shocking water and the resulting portion of washing water of step (b)
High pressure flash is carried out in tower (3), and the Heisui River after high pressure flash is sent to cyclone separator (2) and carries out eddy flow except solid processing；
(d) resulting top clear stream is successively sent to Low Pressure Flashing Column (4) and vacuum flasher (5) after the eddy flow being removed solid processing
It is middle to carry out low pressure flash and vacuum flashing respectively；
(e) by after the vacuum flashing Heisui River and the eddy flow except after solid processing resulting bottom concentrated water send to subsider (6)
Middle carry out settlement treatment；
(f) calcium hydroxide and sodium carbonate is sent into reaction tank (7) to carry out haptoreaction supernatant obtained by the settlement treatment；
(g) Heisui River after the haptoreaction is sent into flocculation basin (8), flocculation treatment is carried out in the presence of flocculant；
(h) Heisui River after the flocculation treatment is sent into sedimentation basin (9) and is settled, will sedimentation gained supernatant successively send to
It is filtered processing and electrodialysis process respectively in filter (10) and electrodialysis reactor (11).
8. according to the method described in claim 7, wherein, in step (c), the eddy flow is except solid processing is so that after high pressure flash
The solid content in Heisui River reduces by 60% or more.
9. method according to claim 7 or 8, wherein in step (e), obtained by the settlement treatment relative to 1t/h
The flow of supernatant, the dosage of calcium hydroxide are 0.08-0.15kg/h, and the dosage of sodium carbonate is 1.3-1.4kg/h；
Preferably, it is 10-50 DEG C that the catalytic condition, which includes: temperature, residence time 30-90min.
10. the method according to any one of claim 7-9, wherein in step (g), the flocculant is inorganic wadding
Solidifying one of agent and organic flocculant or a variety of；
Preferably, the inorganic flocculating agent is one in aluminium polychloride, polyaluminium sulfate, bodied ferric sulfate and poly-ferric chloride
Kind is a variety of；The organic flocculant is one in polyacrylamide, Sodium Polyacrylate, polyvinyl pyridine salt and polyethyleneimine
Kind is a variety of；
Preferably, the flow relative to the Heisui River after the haptoreaction of 1t/h, the dosage of the flocculant are 0.15-
0.2kg/h；
Preferably, it is 10-50 DEG C that the condition of the flocculation treatment, which includes: temperature, residence time 30-60min.
11. method according to any one of claims of claim 7-10, wherein in step (h), the condition packet of the sedimentation
Include: temperature is 10-50 DEG C, time 30-90min；
Preferably, it is 10-40 DEG C that the condition of the filtration treatment, which includes: temperature, time 10-30min；
Preferably, it is 6-6.5 that the condition of the electrodialysis process, which includes: pH value, and temperature is 10-40 DEG C, time 10-30min.
12. the method according to any one of claim 7-11, wherein the solid content in the Heisui River that the coal gasification generates
For 0.5-8 weight %, pH 6-10, Ca2+Content is 150-600mg/L, Mg2+Content is 8-20mg/L, Cl-Content is 90-
300mg/L, SS 80-500mg/L, COD 150-1000mg/L, conductivity are 2000-7000 μ s/cm.
13. the method according to any one of claim 7-12, wherein this method further include:
Part water after the electrodialysis process is sent and is recycled into scrubbing tower (15) and/or gasification furnace (1) by step (i),
It, will be after the reverse osmosis treatment by using the high pressure flash and/or the resulting steam of low pressure flash before preferred steps (i)
Part water deoxygenation processing is carried out in the oxygen-eliminating device (14).
14. according to the method for claim 13, wherein step (i) by after the electrodialysis process 50 weight % or more,
It is recycled it is preferred that the water of 60 weight % or more is sent into scrubbing tower (15) and/or gasification furnace (1).
15. according to the method for claim 13, wherein by the deoxygenation, treated that water send into scrubbing tower (15) is used for
The crude synthesis gas is washed, another part of resulting washing water is back in the gasification furnace (1) as cold shocking water.
16. a kind of coal gasification system, which is characterized in that the system includes:
Gasification furnace (1), for coal to gasify, to obtain crude synthesis gas and containing solid chilled water；
Scrubbing tower (15) obtains net synthesis gas and washing water for washing gasification furnace (1) resulting crude synthesis gas；
High pressure flash tower (3), for carrying out high pressure flash to the Heisui River being used as containing solid cold shocking water and partial washing water；
Cyclone separator (2), for carrying out eddy flow except solid processing to the Heisui River after the high pressure flash；
Sequentially connected Low Pressure Flashing Column (4) and vacuum flasher (5) are used for the eddy flow except resulting top after solid processing
Clear stream successively carries out low pressure flash and vacuum flashing；
Subsider (6), for by after the vacuum flashing Heisui River and the eddy flow except after solid processing resulting bottom concentrated water into
Row settlement treatment；
Reaction tank (7), for supernatant obtained by the settlement treatment and calcium hydroxide and sodium carbonate to be carried out haptoreaction；
Flocculation basin (8), for the Heisui River after the haptoreaction to be carried out flocculation treatment in the presence of flocculant；
Sedimentation basin (9), for settling the Heisui River after the flocculation treatment；
Sequentially connected filter (10) and electrodialysis reactor (11) are successively filtered place for that will settle gained supernatant
Reason and electrodialysis process.
17. system according to claim 16, wherein the system further include: oxygen-eliminating device (14), for by using described
Part water after the electrodialysis process is carried out deoxygenation processing by high pressure flash and/or the resulting steam of low pressure flash.
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| CN110282810A (en) * | 2019-08-01 | 2019-09-27 | 河南晋开化工投资控股集团有限责任公司 | A kind of graywater treating method in coal gasification scouring water recycling system |
| CN111646621A (en) * | 2020-05-27 | 2020-09-11 | 北京清创晋华科技有限公司 | Coal gasification ash water vacuum flash evaporation descaling system |
| CN112624471A (en) * | 2020-12-17 | 2021-04-09 | 华东理工大学 | Short-process coal gasification black water purification method and device |
| CN112897665A (en) * | 2021-04-07 | 2021-06-04 | 宁夏神耀科技有限责任公司 | Method and device for recycling coal gasification wastewater |
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