CN102559288A - Purification method of mixed gas obtained by coal gasification - Google Patents
Purification method of mixed gas obtained by coal gasification Download PDFInfo
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Abstract
The invention provides a purification method of mixed gas obtained by coal gasification. The method comprises the following steps: (1) under a pressurized gasification condition, contacting crushed coal with water so as to obtain crude gas; (2) contacting the crude gas with water so as to quench the crude gas to 200-230 DEG C, further cooling the obtained first gas-phase product to160-190 DEG C, re-cooling the obtained second gas-phase product to below 60 DEG C so as to obtain purified coal gas and a third liquid-phase product, and carrying out oil and water separation on the liquid-phase product so as to obtain phenolic wastewater; and (3) carrying out azeotropy distillation on a mixture containing phenolic wastewater so as to obtain a gas-phase product and a liquid-phase product, wherein the azeotropy distillation condition ensures that a mixture containing water and phenolic wastewater in the gas-phase product contains monophenol azeotrope, and a mixture containing heavy tar and at least part of phenolic wastewater in the liquid-phase product contains polyatomic phenol. By utilizing the method provided by the invention, the wastewater processing difficulty and the wastewater processing cost can be greatly reduced.
Description
Technical field
The invention relates to the purifying method of the gas mixture that a kind of gasification obtains.
Background technology
Coal preparing natural gas technological line is representative with the international coal preparing natural gas of big plain in u.s.a demonstration unit (having moved 20 years) and Datang project at present, mainly adopt the Shandong strange/crushed coal pressure gasifying, the oil resistant of anti-sulphur conversion, low-temperature rectisol purify and methanation.Typical process flow is divided into broken coal, coal dust and coal gangue for first coal with extraction in the colliery carries out the coal choosing, and broken coal is used for pressurized gasification.The principal reaction of crushed coal pressure gasifying is coal and water generation water-gas reaction, and product mainly is carbon monoxide, hydrogen and methane, also has the undecomposed water of part, and a spot of coal tar.The further methanation of carbon monoxide and hydrogen obtains methane gas (being SNG).The content of methane can be up to 96% in the product gas of coal preparing natural gas technology gained, calorific value 35564kJ/m
3More than.
Yet crushed coal pressure gasifying must separate the product raw gas that obtains is separated and purifies through chilling.In the chilling separating technology; The general water that adopts directly contacts water as refrigerant with raw gas, obtain first gas-phase product and the liquid product that contains water and tarry cut; First gas-phase product further cools off and obtains second gas-phase product and the liquid product that contains the middle oil distillate of water then; Continue cooling second gas-phase product, coal gas after being purified and the liquid product that contains water and naphtha fraction carry out oily water separation respectively with above-mentioned liquid phase then; Obtain oil phase and the waste water that contains the heavy tar that phenol, ammonia and part can't remove through oily water separation, the waste water of oil-containing and phenol is mainly by the part oil phase and water is miscible forms.Come from unreacted water in the pressurized gasification reaction because water comprises, also comprise the water that comes from as the chilling agent, therefore, the amount of oily(waste)water is bigger.The aftertreatment of oily(waste)water is generally handled the coal tar of removing wherein through multistage sedimentation; Yet; The oil that also contains nearly 1000mg/L through the water after the multistage sedimentation processing; Also need further to carry out follow-up deamination, dephenolizing process and biochemical treatment again after removing a large amount of coal tar, thereby reach process water reuse or emission standard.But,, be difficult to remove because unit phenol and polyphenol are all soluble in water.The method of dephenolize at present is generally uses solvent-extracted method earlier, through solvent the phenol extraction in the waste water is come out, and the dephenolize waste water after will extracting again afterwards carries out biochemical treatment.Because the cost of biochemical treatment is than higher, and biochemical treatment has relatively high expectations to the total phenol content in the waste water, generally can not surpass 1200mg/L.In addition, biochemical treatment is lower to the removal efficiency of polyphenol and heavy tar.Therefore, generally attempt in solvent extraction process, to extract as far as possible more polyphenol and heavy tar.Yet; When adopting extraction agent to carry out dephenolize, can't take into account removing of polyphenol and unit phenol, and not find the extraction agent that effectively removes polyphenol at present; Even if sacrificed the decreasing ratio of a large amount of unit phenol, also still can not effectivelyly remove polyphenol.The decreasing ratio of existing extraction process dephenolize technology general cell phenol is about 90%, and the decreasing ratio of polyphenol is about 60%.This shows that the processing of oily(waste)water not only causes the water treatment expense to increase, and more increased the difficulty of removing phenol in waste water technology.Even the waste water after handling also is difficult to reach country's one type of emission standard (the COD value is below 100mg/L).Therefore, oily(waste)water is treated as the main weak point of selecting crushed coal pressure gasifying in the coal preparing natural gas project for use.
Summary of the invention
The objective of the invention is in order to overcome the above-mentioned defective of prior art, the purifying method of the gas mixture that a kind of new gasification obtains is provided.
Contriver of the present invention has carried out finding after a large amount of research; Utilize Volatile Phenols in the phenolic wastewater (unit phenol) can form the characteristic of azeotrope with water; When the vp sum of the vp of Volatile Phenols and water vapor surpasses ambient pressure; Phenolic wastewater just comes to life, and promotes Volatile Phenols to change gaseous state over to by liquid state, make Volatile Phenols in the gasiform equilibrium concentration greater than its equilibrium concentration in water.Polyphenol then still is retained in the liquid phase, thereby reaches the purpose that removes polyphenol and heavy tar.In order to solve the oily(waste)water problem of above-mentioned prior art; Contriver of the present invention has carried out a large amount of discovering; After chilling separates and gas-phase product is further cooled off, the mixture of the waste water that obtains is carried out azeotropic distillation, the condition through the control azeotropic distillation makes the form extraction with azeotrope of unit phenol and water; And make the part polyphenol that contains in the mixture of phenolic wastewater be in the said liquid product; And make and only contain unit phenol in the final waste water, or only contain the polyphenol of part except unit phenol, thus greatly reduce the intractability of waste water.
The invention provides the purifying method of the gas mixture that a kind of gasification obtains; Wherein, this method may further comprise the steps: (1) contacts broken coal under the pressurized gasification condition with water; Obtain a kind of raw gas, said raw gas contains synthetic gas, naphtha fraction, diesel oil distillate, tarry cut and water;
(2) the gained raw gas is contacted with water be chilled to 200-230 ℃; Obtain first gas-phase product and first liquid product; First gas-phase product further is cooled to 160-190 ℃; Obtain second gas-phase product and second liquid product, second gas-phase product is cooled to below 60 ℃ once more, coal gas after being purified and the 3rd liquid product; First liquid product, second liquid product and the 3rd liquid product are carried out oily water separation, obtain first phenolic wastewater, second phenolic wastewater and the 3rd phenolic wastewater respectively;
(3) mixture with first phenolic wastewater, second phenolic wastewater and the 3rd phenolic wastewater carries out azeotropic distillation; Obtain gas-phase product and liquid product; The condition of azeotropic distillation makes the polyphenol that the azeotrope that contains the unit phenol that contains in the mixture of water and phenolic wastewater in the said gas-phase product, said liquid product contain heavy tar and contain in the mixture of part phenolic wastewater at least.
The separation method of gasification provided by the invention is through after further cooling off in the chilling separation and to gas-phase product; The mixture of the waste water that obtains is carried out azeotropic distillation, and the condition through the control azeotropic distillation makes unit phenol and water with the form extraction of azeotrope, and makes the part polyphenol that contains in the mixture of phenolic wastewater; The polyphenol of preferred at least 50 weight %; The more preferably polyphenol of at least 80 weight %, the polyphenol that further is preferably 90-100 weight % is in the said liquid product, and makes and only contain unit phenol in the final waste water; Or only contain the polyphenol of part except unit phenol; When adopting conventional method to remove unit phenol or unit phenol and the part polyphenol in the waste water, compared with prior art, greatly reduce the intractability of waste water then.Method provided by the invention can be used to handle various phenolic wastewater, is specially adapted to the processing of high density Volatile Phenols, and the quality that reclaims phenol is good, environmentally friendly.
Description of drawings
Fig. 1 is the technology boiling range figure of purifying method provided by the invention.
Embodiment
According to method provided by the invention; Contain water, phenol, ammonia and heavy tar in the mixture of said first phenolic wastewater, second phenolic wastewater and the 3rd phenolic wastewater; Total phenol content in the said phenolic wastewater is generally 4500-6500mg/L; The content of heavy tar is 200-3000mg/L, and ammonia content is 2000-8000mg/L.Said total phenol comprises Volatile Phenols again (promptly; Unit phenol; Unit phenol is meant the aldehydes matter that has only a hydroxyl that directly links to each other on the aromatic ring) and non-volatile phenol (that is, polyphenol, polyphenol are meant that aromatic ring has the aldehydes matter of the hydroxyl that directly links to each other more than); The content of said Volatile Phenols (unit phenol) is generally 3000-4500mg/L, and the content of non-volatile phenol (polyphenol) is generally 1500-2000mg/L.
Wherein, Said aldehydes matter mainly comprises phenol, cresols, naphthols and their verivate; As 2; 5-xylenol, 2; 4-xylenol, 2-propylene phenol, 3-ethyl-5 methylphenol, 2-ethyl-5-methylphenol, 3,5-xylenol, ortho-methyl phenol, 2-methyl hydroquinone, 2-methylresorcinol, 3-methyl pyrocatechol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, p-methyl phenol, m-methyl phenol, naphthyl alcohol, 2-methyl isophthalic acid-naphthols.
The mensuration of said total phenol content and the measuring method of volatile phenol concentrations presented are as well known to those skilled in the art.For example, the mensuration of total phenol content can be with reference to " water and effluent monitoring analytical procedure " the 4th edition, and State Environmental Protection Administration writes, and the China Environmental Science Press publishes; The mensuration of said volatile phenol concentrations presented can be with reference to GB 7491-87 or HZ 502-2009, and the content that total phenol content deducts Volatile Phenols is substantially equal to the content of non-volatile phenol, perhaps adopts gc (GCMS) to measure the content of non-volatile phenol.
According to the present invention, because the boiling point of polyphenol is generally more than 230 ℃, except nitrophenols; The boiling point of unit phenol generally all is lower than 230 ℃, therefore, and for can be when the azeotropic distillation; Make the unit phenol that contains in the mixture of water and phenolic wastewater form azeotrope; And the polyphenol that contains in the part phenolic wastewater at least is retained in the said liquid product, and just need the condition of control azeotropic distillation, make Volatile Phenols (unit phenol) and water form azeotrope from the cat head extraction; And make part polyphenol at least; The polyphenol of preferred at least 50 weight %, the more preferably polyphenol of at least 80 weight %, the polyphenol of further preferred 90-100 weight % is retained in the liquid product at the bottom of the tower.
According to the present invention; Phenolic wastewater is carried out azeotropic distillation in azeotropy rectification column, carry out, that is, phenolic wastewater is heated to more than the boiling point of water; Phenolic wastewater sent into carry out azeotropic distillation in the azeotropy rectification column; Said azeotropic distillation condition make unit phenol and water with the form of azeotrope from the cat head extraction, part polyphenol and heavy tar extraction at the bottom of the tower at least, thus can reach the purpose that phenolic wastewater purifies.
According to the present invention, the condition of said azeotropic distillation comprises that pressure is the 0.1-4 MPa, is preferably the 0.1-0.5 MPa, further is preferably the 0.1-0.2 MPa.The temperature of cat head can be 105-210 ℃, is preferably 105-150 ℃, further is preferably 105-125 ℃; Temperature at the bottom of the tower can be 125-320 ℃, is preferably 125-220 ℃, further is preferably 125-150 ℃.At pressure is under the 0.1-4 MPa; The polyphenol that can guarantee at least 50 weight % when the temperature of cat head is 105-210 ℃ is in the said liquid product (under the tower top temperature condition with higher; Higher tower top temperature can make the gasification of part polyphenol and change in the gas-phase product); Under the preferable case, be under the 0.1-0.5 MPa, can guarantee when the temperature of cat head is 105-150 ℃ that polyphenol greater than at least 80 weight % is in the said liquid product (in the said temperature scope, possibly also have few part polyphenol gasification and change in the gas-phase product) at pressure; More preferably under the situation; Under the 0.1-0.2 MPa, when the temperature of cat head is 105-125 ℃, can guarantee that the polyphenol of 90-100 weight % is in the said liquid product.
According to the present invention, the condition of said azeotropic distillation can also comprise reflux ratio, and said reflux ratio can be 1-5: 1, be preferably 1-3: 1.
According to the present invention, said azeotropy rectification column can be packing tower, also can be tray column, can also be filler and board-like compound tower.
The filler that is loaded in the said packing tower can be for well known to a person skilled in the art various fillers, and for example this filler can be selected from one or more in Raschig ring, Pall ring, cascade ring, saddle type ring, arc saddle type, square saddle type, Dixon ring, Cannon ring, Lamb wave line and the net corrugated regular filler.
In bubble-cap, sieve plate, inclined hole, the float valve one or more can be installed in said tray column.
In order to obtain the ideal separating effect, said azeotropy rectification column preferably has certain stage number or theoretical plate number, and for example, its stage number or theoretical plate number can be the 6-18 piece, are preferably the 8-13 piece.
According to the present invention, said azeotropy rectification column can adopt and well known to a person skilled in the art various separation columns, and for example, said separation column can be made up of body of the tower, tower still, tower still reboiler, cat head water cooler and return tank of top of the tower (phase-splitting).
According to the present invention, owing to contain a large amount of ammonia in the said phenolic wastewater, therefore; After sending into phenolic wastewater in the azeotropy rectification column; And the ammonia in the said phenolic wastewater is changed in the gas-phase product, under the preferable case, this method also comprises the waste water of from gas-phase product, isolating ammonia and containing unit phenol; And with the water-soluble ammoniacal liquor that obtains of ammonia, to reach the purpose that removes the ammonia in the waste water.
The said method of from gas-phase product, isolating ammonia and phenolic wastewater can for example, will further be cooled off from the gas-phase product that cat head is overflowed for the conventional various separation methods in this area; The refrigerative temperature is so that water is liquid, and ammonia keeps gaseous state, preferably is cooled to 50-90 ℃; Further preferred 70-90 ℃; Realize gas-liquid separation simultaneously, collect and obtain ammonia and phenolic wastewater, the ammonia ammoniacal liquor that promptly obtains soluble in water.Can realize removing the purpose of free ammonia like this.
Phenol in the said phenolic wastewater can all be unit phenol or only contain the part polyphenol that therefore, the process of removing the phenol in the waste water becomes relatively easy.The method of removing the phenol in the waste water can adopt and well known to a person skilled in the art that the whole bag of tricks carries out.
The waste water that the method for employing prior art obtains need carry out can satisfying after dephenolize is handled the water quality requirement of biochemical treatment earlier; Usually the COD value of waste water is that 5500mg/L, total phenol content are below 1200mg/L; Because the content of polyphenol and heavy tar is still higher in the waste water; Therefore, will satisfy after the biochemical treatment that to make that the COD value of waste water is reduced to below the 100mg/L still difficult, and the waste water that adopts the method that waste water is handled of the present invention to obtain preferably only contains unit phenol; Therefore; Waste water satisfies the condition of directly carrying out extracting and dephenolizing or biochemical treatment, and the COD value of wherein directly carrying out the waste water of biochemical treatment can reach 10,000 mg/L, and the processing efficiency of waste water is higher.
Among the present invention, the starting temperature of said raw gas is not special to be limited, and is generally 350-750 ℃, is preferably 350-650 ℃; Pressure is generally the 1-8 MPa, is preferably the 2-6 MPa, further is preferably the 2-4 MPa.Among the present invention, said raw gas is preferably the crushed coal pressure gasifying product especially.In the said raw gas, be benchmark with the total amount of synthetic gas and tar, the content of synthetic gas is generally 80-99 weight %, is preferably 80-95 weight %, and the content of tar is generally 0.1-20 weight %, is preferably 0.5-15 weight %.The content of said water is the 10-60 weight % of said raw gas, is preferably 15-50 weight %.
Among the present invention, the staple of the synthetic gas in the said raw gas is carbon monoxide and hydrogen, also comprises in addition being gasiform component such as methane, ethane, propane, different propane, carbonic acid gas, hydrogen sulfide, ammonia, N under the normal temperature
2In one or more.Among the present invention, said tar is continued to use the conventional definition in this area, the thick coal tar that the expression boiling point is high, viscosity is big.Except water, synthetic gas and tar, also comprise in the said raw gas under the normal temperature for liquid liquid ingredient such as phenol, biphenol, formic acid, gasoline, boiling point being lower than in 180 ℃ the petroleum naphtha one or more.Therefore these components all can gasify under the condition of said contact owing to more volatile, all will escape in the gas-phase product with gas form.
According to separation method provided by the invention, the gained raw gas contacted with water be chilled to 200-230 ℃, can realize tentatively raw gas cooling and the effect that purifies.With the gained raw gas with obtain first gas-phase product and first liquid product after water contacts chilling, wherein, the raw gas of said first gas-phase product for tentatively being cooled and purifying, first liquid product is the mixture of water and tarry cut.The condition of said contact comprises that also the consumption of said water can be 1-15 times of said raw gas weight, and the time of contact can be realized above-mentioned cooling temperature for 1-30 second.
Then; First gas-phase product further is cooled to 160-190 ℃; With with further cooling and the purification of first gas-phase product, obtain second gas-phase product and second liquid product, wherein; The raw gas of said second gas-phase product for further being cooled and purifying, second liquid product is the mixture of water and diesel oil distillate.Then, second gas-phase product is cooled to below 60 ℃ once more, is preferably 35-50 ℃, with the further cooling and purifying of second gas-phase product, coal gas after being purified and the 3rd liquid product, wherein, the 3rd liquid product is the mixture of water and naphtha fraction.
Among the present invention, unless stated otherwise, said gasification latent heat is meant 1 gasification latent heat under the normal atmosphere.Boiling point is meant the boiling point under the standard state.
According to method provided by the invention, the said mode that contacts with water can be the various cooling ways of contact, for example, can be counter current contact or and stream contact or adverse current and the stream mode of carrying out simultaneously.
According to the present invention; First liquid product, second liquid product and the 3rd liquid product are carried out oily water separation; The method that obtains first phenolic wastewater, second phenolic wastewater and the 3rd phenolic wastewater respectively can be the oil-water separation method of routine, for example, and the sedimentation standing methods.
Because the present invention only relates to the improvement to the separation method of pressurized gasification product, therefore, the preparation method of said raw gas can be a method well known in the art, for example, can adopt crushed coal pressure gasifying method well known in the art to obtain.Said broken coal can be that size is not less than 5 millimeters various broken coal pieces, and for example size is the broken coal piece of 2-50 millimeter.Said pressurized gasification condition comprises that outlet raw gas temperature is 350-750 ℃, is preferably 350-650 ℃, and pressure can be the 1-8 MPa, is preferably the 2-6 MPa, further is preferably the 2-4 MPa.Said pressurized gasification can carry out in the various vapourizing furnaces known in the art, for example, carries out in lurgi gasifier or the crushed coal pressurized-gasification furnace.
According to one embodiment of the present invention, the purifying method of the gas mixture that said gasification obtains is as shown in Figure 1.Raw gas directly contacted with water in gas-liquid separator such as chilling separator carry out chilling; Obtain first gas-phase product and first liquid product; The raw gas of said first gas-phase product for tentatively being cooled and purifying, first liquid product is the mixture of water and tarry cut; Then, first gas-phase product is further cooled off, obtain second gas-phase product and second liquid product, the raw gas of said second gas-phase product for further being cooled and purifying, second liquid product is the mixture of water and diesel oil distillate; Then, second gas-phase product is cooled off once more, coal gas after being purified and the 3rd liquid product, wherein, the 3rd liquid product is the mixture of water and naphtha fraction.With above-mentioned first liquid product that obtains, second liquid product and the 3rd liquid product carry out oily water separation, obtain first phenolic wastewater respectively, second phenolic wastewater and the 3rd phenolic wastewater; Above-mentioned phenolic wastewater mixing is obtained composite waste; And said composite waste sent into carry out azeotropic distillation in the azeotrope column; Obtain gas-phase product from cat head; Contain the azeotrope of the unit phenol that contains in water and the phenolic wastewater in the said gas-phase product, at the bottom of tower, obtain liquid product, the polyphenol that said liquid product contains heavy tar and contains in the part phenolic wastewater at least; In interchanger further after the cooling, the promoting the circulation of qi liquid of going forward side by side separates with said gas-phase product, obtains ammonia (the water-soluble ammoniacal liquor that obtains) and only contains unit phenol and perhaps also contain the waste water after the processing of part polyphenol except unit phenol.
Following embodiment will do further explanation to the present invention.
Embodiment 1
The purifying method of the gas mixture that this embodiment is used to explain that gasification provided by the invention obtains.
Adopt technology shown in Figure 1; Water vapor is carried out pressurized gasification with big or small sending at 1: 1 with weight ratio for the brown coal broken coal of 5-50 millimeter (relevant rerum natura sees table 1 for details) in the vapourizing furnace; The bottom temp of vapourizing furnace is 1200 ℃; Head temperature is 500 ℃, and base pressure is 3.5MPa, and top pressure is 3MPa; Obtain pressure and be 3MPa, temperature and be the gas mixture that 500 ℃ crushed coal pressure gasifying product promptly contains tar and discharge (composition outside dewatering is as shown in table 2, and the content of water is 30 weight % of crushed coal pressure gasifying product total amount) from top of gasification furnace.
Be that 3 MPas, temperature are that 500 ℃ crushed coal pressure gasifying product is that 200 ℃, flow are that 800 kilograms/hour water contacts in the chilling separator and carries out chilling with 1000 kilograms/hour flow and temperature with this pressure then; Contact after 25 seconds, make the temperature of said raw gas be reduced to 220 ℃, obtain first gas-phase product and first liquid product; First gas-phase product further is cooled to 190 ℃; Obtain second gas-phase product and second liquid product, second gas-phase product is cooled to 55 ℃ once more, coal gas after being purified and the 3rd liquid product; First liquid product, second liquid product and the 3rd liquid product are carried out oily water separation; Obtain first phenolic wastewater, second phenolic wastewater and the 3rd phenolic wastewater respectively, and first phenolic wastewater, second phenolic wastewater and the 3rd phenolic wastewater are mixed, obtain composite waste;
Above-mentioned composite waste (content of unit phenol, polyphenol, ammonia and heavy tar is as shown in table 3 in the composite waste) sent into carry out rectifying separation in the azeotropy rectification column; The operational condition of azeotropy rectification column comprises that pressure is 0.4 MPa; Tower top temperature is 135 ℃; Tower still temperature is 200 ℃, and reflux ratio is 2: 1, and the stage number of azeotropy rectification column is 10;
From azeotropic distillation column overhead extraction gas-phase product, wherein, the content of polyphenol is 83 weight % of the content of the polyphenol that contains in the phenolic wastewater the mixture of extraction at the bottom of the azeotropic distillation Tata;
To be cooled to 70 ℃ from the gas-phase product of cat head extraction, the waste water after isolating ammonia and handling, ammonia is dissolved in the water obtains ammoniacal liquor; The content of unit phenol is 2500mg/L in the waste water; The content of polyphenol is 204mg/L, and ammonia content is 1650mg/L, and heavy tar content is 0mg/L.
Embodiment 2
The purifying method of the gas mixture that this embodiment is used to explain that gasification provided by the invention obtains.
Adopt technology shown in Figure 1; Water vapor is carried out pressurized gasification with big or small sending at 1: 1 with weight ratio for the brown coal broken coal of 5-50 millimeter (relevant rerum natura sees table 1 for details) in the vapourizing furnace; The bottom temp of vapourizing furnace is 1000 ℃; Head temperature is 300 ℃, and base pressure is 3MPa, and top pressure is 2.5MPa; The crushed coal pressure gasifying product that obtains pressure and be 2.5 MPas, temperature and be 300 ℃ is discharged (composition outside dewatering is as shown in table 2, and the content of water is 50 weight % of crushed coal pressure gasifying product total amount) from the top.
Be that 2.5 MPas, temperature are that 300 ℃ crushed coal pressure gasifying product is that 150 ℃, flow are that 1200 kilograms/hour water contacts in the chilling separator with 1500 kilograms/hour flow and temperature with this pressure then; Contact (condition of contact makes the temperature of said raw gas be reduced to 200 ℃) after 20 seconds; Obtain first gas-phase product and first liquid product; First gas-phase product further is cooled to 160 ℃; Obtain second gas-phase product and second liquid product, second gas-phase product is cooled to 40 ℃ once more, coal gas after being purified and the 3rd liquid product; First liquid product, second liquid product and the 3rd liquid product are carried out oily water separation; Obtain first phenolic wastewater, second phenolic wastewater and the 3rd phenolic wastewater respectively, and first phenolic wastewater, second phenolic wastewater and the 3rd phenolic wastewater are mixed, obtain composite waste;
Above-mentioned composite waste (content of unit phenol, polyphenol, ammonia and heavy tar is as shown in table 3 in the composite waste) sent into carry out rectifying separation in the azeotropy rectification column; The operational condition of azeotropy rectification column comprises that pressure is 0.2 MPa; Tower top temperature is 115 ℃; Tower still temperature is 140 ℃, and reflux ratio is 3: 1, and the stage number of azeotropy rectification column is 13;
From azeotropic distillation column overhead extraction gas-phase product, wherein, the content of polyphenol is 90 weight % of the content of the polyphenol that contains in the phenolic wastewater the mixture of extraction at the bottom of the azeotropic distillation Tata;
To be cooled to 80 ℃ from the gas-phase product of cat head extraction, the waste water after isolating ammonia and handling, ammonia is dissolved in the water obtains ammoniacal liquor; The content of unit phenol is 2500mg/L in the waste water; The content of polyphenol is 120mg/L, and ammonia content is 1500mg/L, and heavy tar content is 0mg/L.
Embodiment 3
The purifying method of the gas mixture that this embodiment is used to explain that gasification provided by the invention obtains.
Adopt technology shown in Figure 1; Water vapor is carried out pressurized gasification with big or small sending at 1: 1 with weight ratio for the brown coal broken coal of 5-50 millimeter (relevant rerum natura sees table 1 for details) in the vapourizing furnace; The bottom temp of vapourizing furnace is 1300 ℃; Head temperature is 650 ℃, and base pressure is 4MPa, and top pressure is 3.5MPa; The crushed coal pressure gasifying product that obtains pressure and be 3.5 MPas, temperature and be 650 ℃ is discharged (composition outside dewatering is as shown in table 2, and the content of water is 20 weight % of crushed coal pressure gasifying product total amount) from the top.
Be that 3.5 MPas, temperature are that 650 ℃ crushed coal pressure gasifying product is that 80 ℃, flow are that 550 kilograms/hour water contacts in the chilling separator with 800 kilograms/hour flow and temperature with this pressure then; Contact (condition of contact makes the temperature of said raw gas be reduced to 210 ℃) after 15 seconds; Obtain first gas-phase product and first liquid product; First gas-phase product further is cooled to 190 ℃; Obtain second gas-phase product and second liquid product, second gas-phase product is cooled to 35 ℃ once more, coal gas after being purified and the 3rd liquid product; First liquid product, second liquid product and the 3rd liquid product are carried out oily water separation; Obtain first phenolic wastewater, second phenolic wastewater and the 3rd phenolic wastewater respectively, and first phenolic wastewater, second phenolic wastewater and the 3rd phenolic wastewater are mixed, obtain composite waste;
Above-mentioned composite waste (content of unit phenol, polyphenol, ammonia and heavy tar is as shown in table 3 in the composite waste) sent into carry out rectifying separation in the azeotropy rectification column; The operational condition of azeotropy rectification column comprises that pressure is 0.1 MPa; Tower top temperature is 105 ℃; Tower still temperature is 128 ℃, and reflux ratio is 3: 1, and the stage number of azeotropy rectification column is 8;
From azeotropic distillation column overhead extraction gas-phase product, wherein, the content of polyphenol is 99 weight % of the content of the polyphenol that contains in the phenolic wastewater the mixture of extraction at the bottom of the azeotropic distillation Tata;
To be cooled to 80 ℃ from the gas-phase product of cat head extraction, the waste water after isolating ammonia and handling, ammonia is dissolved in the water obtains ammoniacal liquor; The content of unit phenol is 2500mg/L in the waste water; The content of polyphenol is 12mg/L, and ammonia content is 1500mg/L, and heavy tar content is 0mg/L.
Table 1
Annotate:
War---represent coal-fired as received basis moisture; Wad---the coal-fired dry basic moisture of expression; Har---represent coal-fired as received basis hydrogen branch; Aad---the coal-fired dry basic ash content of expression; Vad---the coal-fired dry basic volatile matter of expression; Sad---the coal-fired dry basic sulphur content of expression; Car---represent coal-fired as received basis carbon branch; Oar---represent coal-fired as received basis oxygen branch; Nar---represent coal-fired as received basis nitrogen branch; Sar---represent coal-fired as received basis sulphur content; T1---softening temperature, ℃; T2---hemispherical temperature, ℃; T3---melt temperature, ℃.
Table 2
| Form (weight %) | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| H 2 | 3.59 | 3.61 | 3.58 |
| CO | 19.68 | 19.75 | 19.56 |
| CO 2 | 62.88 | 63.09 | 62.71 |
| CH 4 | 7.57 | 7.35 | 7.65 |
| N 2 | 0.34 | 0.34 | 0.34 |
| C 2 | 0.39 | 0.36 | 0.39 |
| C 3 | 0.39 | 0.35 | 0.39 |
| H 2S | 0.50 | 0.50 | 0.51 |
| NH 3 | 0.17 | 0.17 | 0.17 |
| HCN | 0.01 | 0.01 | 0.01 |
| With C 6H 6The O meter, unit phenol content | 0.39 | 0.39 | 0.39 |
| With C 6H 6O 2Meter, polyphenol content | 0.26 | 0.26 | 0.26 |
| Boiling point is less than 180 ℃ cut | 0.41 | 0.38 | 0.41 |
| Boiling point is 180-360 ℃ a cut | 1.60 | 1.57 | 1.70 |
| Boiling point is greater than 360 ℃ cut | 1.82 | 1.87 | 1.93 |
| ∑ | 100.00 | 100.00 | 100.00 |
| The oil product total amount | 4.48 | 4.47 | 4.69 |
Table 3
| Waste water composition | Content (mg/L) |
| Unit phenol | 2500 |
| Polyphenol | 1200 |
| Ammonia | 5500 |
| Heavy tar | 3000 |
Claims (11)
1. the purifying method of the gas mixture that obtains of a gasification is characterized in that this method may further comprise the steps:
(1) under the pressurized gasification condition, broken coal is contacted with water, obtain a kind of raw gas, said raw gas contains synthetic gas, naphtha fraction, diesel oil distillate, tarry cut and water;
(2) the gained raw gas is contacted with water be chilled to 200-230 ℃; Obtain first gas-phase product and first liquid product; First gas-phase product further is cooled to 160-190 ℃; Obtain second gas-phase product and second liquid product, second gas-phase product is cooled to below 60 ℃ once more, coal gas after being purified and the 3rd liquid product; First liquid product, second liquid product and the 3rd liquid product are carried out oily water separation, obtain first phenolic wastewater, second phenolic wastewater and the 3rd phenolic wastewater respectively;
(3) mixture with first phenolic wastewater, second phenolic wastewater and the 3rd phenolic wastewater carries out azeotropic distillation; Obtain gas-phase product and liquid product; The condition of azeotropic distillation makes the polyphenol that the azeotrope that contains the unit phenol that contains in the mixture of water and phenolic wastewater in the said gas-phase product, said liquid product contain heavy tar and contain in the mixture of part phenolic wastewater at least.
2. method according to claim 1, wherein, the condition of azeotropic distillation makes at least 50 weight % of the polyphenol that contains in the mixture of phenolic wastewater be in the said liquid product.
3. method according to claim 2, wherein, the condition of azeotropic distillation makes at least 80 weight % of the polyphenol that contains in the mixture of phenolic wastewater be in the said liquid product.
4. method according to claim 3, wherein, the condition of azeotropic distillation makes the 90-100 weight % of the polyphenol that contains in the mixture of phenolic wastewater be in the said liquid product.
5. according to any described method among the claim 1-4, wherein, the mixture of phenolic wastewater to be carried out azeotropic distillation in azeotropy rectification column, carry out, the condition of said azeotropic distillation comprises that pressure is the 0.1-4 MPa; The temperature of cat head is 105-210 ℃, and the temperature at the bottom of the tower is 125-320 ℃.
6. method according to claim 5, wherein, pressure is the 0.1-0.5 MPa; The temperature of cat head is 105-150 ℃, and the temperature at the bottom of the tower is 125-220 ℃.
7. method according to claim 6, wherein, pressure is the 0.1-0.2 MPa; The temperature of cat head is 105-125 ℃, and the temperature at the bottom of the tower is 125-150 ℃.
8. method according to claim 4, wherein, the theoretical plate number of said azeotropy rectification column is the 6-18 piece, reflux ratio is 1-5: 1.
9. method according to claim 7, wherein, the theoretical plate number of said azeotropy rectification column is the 8-13 piece, reflux ratio is 1-3: 1.
10. method according to claim 4 wherein, also contains ammonia in the said gas-phase product, this method also comprises the waste water of from gas-phase product, isolating ammonia and containing unit phenol, and with the water-soluble ammoniacal liquor that obtains of ammonia.
11. method according to claim 1, wherein, said broken coal is that size is that the coal cinder of 2-50 millimeter, the condition of said pressurized gasification comprise that gas outlet temperature is 350-750 ℃, and pressure is the 1-8 MPa.
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| CN114395429A (en) * | 2022-01-20 | 2022-04-26 | 青岛君扬化工科技有限公司 | Low-rank coal dry distillation gas separation device and process |
| CN115058265A (en) * | 2022-06-02 | 2022-09-16 | 国家能源集团煤焦化有限责任公司 | Device and method for recovering chemical products from coke oven gas |
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