CN1307626A - Gasification method - Google Patents
Gasification method Download PDFInfo
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- CN1307626A CN1307626A CN 99807937 CN99807937A CN1307626A CN 1307626 A CN1307626 A CN 1307626A CN 99807937 CN99807937 CN 99807937 CN 99807937 A CN99807937 A CN 99807937A CN 1307626 A CN1307626 A CN 1307626A
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- nickel
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
- C10K1/105—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids containing metal compounds other than alkali- or earth-alkali carbonates, -hydroxides, oxides, or salts of inorganic acids derived from sulfur
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
- C10K1/26—Regeneration of the purifying material contains also apparatus for the regeneration of the purifying material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
Abstract
A method for removing a cyanide component by or in application of steam stripping while suppressing the formation of a nickel-cyanide complex. A mixture of a raw material and sulfur is fed to a gasification step (101) in a way such that the mixture has a sulfur content of 0.5 to 2.0 wt. % and is gasificated. The resultant crude gas is washed in a cooling/carbon washing step (102), wherein nickel sulfide or the like is preferentially formed in a drain water and the formation of a nickel-cyanide complex is suppressed. A cyanide component is emitted as HCN. Alternatively, to stripper (201), drain water is introduced from line (210), a strong acid from line (211) and steam from line (212). A nickel-cyanide complex contained in a drain water having a controlled pH of 2.0 to 6.0 is decomposed to a cyanide ion and a nickel ion. The cyanide ion is finally emitted as HCN from line (216), and a nickel ion is discharged from line (217) and treated as nickel hydroxide.
Description
Technical field
The present invention relates to a kind of gasification process of nickeliferous and sulphur raw material, in more detail, relate to a kind of like this gasification process, coal or refining of petroleum are obtained comprise heavy oil, long residuum, vacuum residuum or bituminous heavy wet goods and adopt partial oxidation process to gasify the time, this method can suppress to cool off the generation of the nickel-cyano complex in the waste water that the carbon washing procedure produces.
In addition, the present invention relates to a kind of combination has the gasification process of method of wastewater treatment, in more detail, the present invention is combined to the wastewater treatment method that comprises the nickeliferous-cyano complex (cyanic acid nickel ion) that produces when heavy oil, long residuum, vacuum residuum or bituminous heavy wet goods adopt the partial oxidation process gasification of coal or refining of petroleum acquisition in the gasification process.
Background technology
At refining of petroleum residual oil such as the coal that will contain heavy metals such as hydrogen, carbon, nitrogen, sulphur and Ni-V-Fe and mink cell focus, long residuum, vacuum residuum, pitches as raw material, the operation that oxygen of supplying with air separation plant and the steam of supplying with from the outside at high temperature gasify, according to the composition in the raw material, except generating hydrogen, carbon monoxide, carbonic acid gas and methane, also generate hydrogen sulfide, carbonyl sulfide, prussic acid and ammonia etc. as by product.
The hydrogen sulfide content that generates in the gasification process than prussic acid for a long time, in the heavy metal particularly nickel and iron generate carbonyl compound, but in cooling carbon washing procedure subsequently, the existence of hydrogen sulfide makes its major part be transformed into nickelous sulfide or iron sulphide, discharges with the carbon slurry.
Nickelous sulfide in the waste water or iron sulphide can precipitate and separate, and precipitation has been removed in the waste water of nickel etc., and cyanogen and ammonia exist with ionic species.But, before supplying with final wastewater treatment operation, can adopt common pretreatment process (for example stripping) with cryanide ion as prussic acid, ammonium ion as ammonia, stripping separates to remove and reaches environmentally safe degree (according to the restriction of cyanogen total amount, the discharging of cyanide wastewater is subjected to water pollution to prevent forbidding of method from waste water.)。In addition, nickel can be subjected to chemical treatment in the wastewater treatment operation, remove as oxyhydroxide.
But the composition difference in the raw material (for example few raw material of sulphur content) can make the hydrogen cyanide content that generates in the gasification process more than hydrogen sulfide, and therefore, when using the raw material of this composition, the nickel in the waste water preferentially generates nickel-cyano complex, rather than generates nickelous sulfide.
Because therefore nickel-cyano complex, before supplying with final wastewater treatment operation, only adopts stripping to be difficult to remove cyanogen make pH keep existing as the cyanic acid nickel ion in the waste water of alkalescence because of containing ammonia highly stablely.
Disclosure of an invention
The invention provides a kind of gasification process, this method can make the processing of subsequent handling carry out more easily by suppressing the generation of the nickel-cyano complex in the waste water behind the cooling carbon washing procedure.
In addition, the invention provides a kind of gasification process, when employed raw material makes the hydrogen cyanide content that generates in the gasification process than hydrogen sulfide for a long time, made up and to have removed nickel-cyano complex of containing in the waste water method of wastewater treatment to environmentally safe degree.
When stably containing nickel-cyano complex in the waste water after the gasification process, even adopt conventional vaporizing extract process to be removed fully, present inventors are conceived to this point and have carried out research repeatedly, its result, established a kind of so effective commercial run that uses vaporizing extract process, this method is by in cooling carbon washing procedure precipitable isolating nickelous sulfide or other sulfide preferentially being generated, suppress the generation of nickel-cyano complex, can be reduced to degree to cyanogen content the environment completely safe.
In addition, owing to the pH of waste water remains alkalescence nickel-cyano complex is stably existed, even using conventional vaporizing extract process can not be removed fully, present inventors are conceived to this point and have carried out research repeatedly, its result, established a kind of so effective commercial run that uses vaporizing extract process, this method is to remain in the acid range by the pH value with waste water, can remove cyanogen to the degree to the environment completely safe.
Gasification process of the present invention is that the vaporized raw material of wanting of the sulphur of a kind of nickel that will contain 10～100 ppm by weight and 0.1～1.0 weight % adopts partial oxidation process carry out gasification process, through overcooling, carbon washing, desulfurization, obtain the method for thick gas resultant, it is characterized in that
From the waste water of washing procedure, reclaim carbon,
(1) sulphur is mixed into wants in the vaporized raw material, its consumption is to make the hydrogen sulfide content that generates in the gasification process more than prussic acid, and waste water is carried out stripping handle, perhaps
(2) will contain waste water in the washing procedure of nickel-cyano complex and in 1 above stripping tower, carry out stripping when handling, in stripping tower, supply with acid, so that the pH value of waste water is adjusted to 2.0～6.0, thus nickel-cyano complex is resolved into nickel ion and cryanide ion, nickel ion is processed as nickel hydroxide, and cryanide ion is processed as prussic acid.
Preferably, vaporized raw material is heavy oil, long residuum, vacuum residuum or the pitch that coal or refining of petroleum obtain.
Preferably, sulphur content is 0.5～2.0 weight %.
Preferably, the sulphur that is mixed in the raw material is to contain sour gas that concentrates the hydrogen sulfide of removing in the desulfurization process or the sulfur-bearing thing of supplying with from the outside.
Preferably, when in 1 stripping tower, handling, use inner column plate section, supply with waste water, supply with acid to bottom column plate section to the upper tray section by upper tray section and 2 sections stripping towers that constitute of bottom column plate section.
Preferably, when handling in 2 above stripping towers, the column plate section of each stripping tower inside constitutes by 1 section, supplies with waste water from the column plate section top of the 1st stripping tower, mixing acid in the waste water that discharge the 1st stripping tower below supplies to above the column plate section of the 2nd stripping tower then.
Preferably, the carbon that has washed is recovered in the gasification process.
Foregoing invention scheme (1) is a kind of like this gasification process, it is characterized in that, the partial oxidation process that employing is made of gasification process, cooling carbon washing procedure, desulfurization process, carbon recovery process and stripping operation, to nickel content is that 10～100 ppm by weight and sulphur content are that the raw material of 0.1～1.0 weight % is when gasifying, sulphur is mixed in the raw material of supplying with gasification process, so that the hydrogen sulfide content that generates in the gasification process is more than prussic acid.
Foregoing invention scheme (2) incorporates into method in the gasification process for a kind of with method of wastewater treatment, it is characterized in that, the waste water that will contain heavy metal ion, cyanogen, ammonia, carbonic acid gas, hydrogen sulfide and nickel-cyano complex carries out stripping when handling in the stripping tower more than 1, in stripping tower, supply with acid, so that the pH value of waste water is adjusted to 2.0～6.0, thus nickel-cyano complex is resolved into nickel ion and cryanide ion, nickel ion is processed as nickel hydroxide, and cryanide ion is processed as prussic acid.This method of wastewater treatment below is described.
Simple declaration to accompanying drawing
Fig. 1 is the process flow diagram of embodiment of the present invention (1).
Fig. 2 is for also having made up the invention embodiment (1) of method of wastewater treatment and the process flow diagram of (2).
Fig. 3 is the process flow diagram of a scheme of invention embodiment (2).
Fig. 4 is the process flow diagram of another program of invention embodiment (2).
The preferred version that carries out an invention
Be applicable to that nickel content is 10～100 ppm by weight in the raw material (hereinafter referred to as " gasified raw material ") of gasification process of the present invention, sulphur content is 0.1～1.0 weight %.Fossil feedstock beyond this scope, for example nickel content is that 100 ppm by weight, sulphur content are under the occasion of 2.0 weight %, because the growing amount of nickel-cyano complex is considerably less, can not obtain effect of the present invention.As this gasified raw material, can enumerate heavy oil, long residuum, vacuum residuum or pitch that coal or refining of petroleum obtain, the raw material that they are Duoed than hydrogen sulfide for the hydrogen cyanide content that generates in gasification reaction.
Prerequisite of the present invention is, when making gasified raw material through gasification process, cooling carbon washing procedure, desulfurization process, carbon recovery process and cyanogen stripping operation, with quantitative sulphur be mixed in the gasified raw material of supplying with gasification process, if but satisfy this prerequisite, the technician constitutes the common change of making to other and is also contained among the present invention.Below based on the embodiment of description of drawings gasification process of the present invention.Fig. 1 is the process flow diagram of embodiment of the present invention (1).
Gasified raw materials such as vacuum residuum through the refining of petroleum acquisition, the amount of about 50 weight % is supplied with gasification reaction operation 101 by pipeline 111, the amount of about in addition 50 weight % is supplied with carbon recovery process 104 by pipeline 111 through pipeline 124, so that the carbon that reclaims in the carbon recovery process 104 has flowability.At this moment, sulphur is mixed in the gasified raw material of supplying with gasification reaction operation 101.
The combined amount of sulphur is the amount that the hydrogen sulfide content that generates in the gasification process is Duoed than prussic acid, for example, is preferably 0.5～2.0 weight % of the mixture of gasified raw material and sulphur, is preferably 1.0～2.0 weight % especially.Sulphur content in the mixture is when 0.5 weight % is above, and the generation that can suppress to cool off the nickel-cyano complex in the carbon washing procedure waste water when 2.0 weight % are following, when having above-mentioned effect, can also alleviate the desulfurization burden in the desulfurization process.
There is no particular limitation in institute's blended sulphur source in the gasified raw material, considers from the viewpoint of efficent use of resources, preferably draws from pipeline 117 concentrating the sour gas of removing that contains hydrogen sulfide in the desulfurization process 103, supplied with by pipeline 118.In addition, in only utilizing desulfurization process 103, concentrate when the sour gas of removing is very difficult to be adjusted to appropriate amount with the sulphur content in the mixture, and start of run be can not supply with sour gas by desulfurization process 103 time, can supply with solid-state, liquid state or gasiform sulphur or sulfide from the outside.
So, in the gasification reaction operation 101 of supplying with gasified raw material and sulphur, supply with about 380～400 ℃ steam, supply with by the extraneous air tripping device is isolating by pipeline 113 and be heated to about 160～230 ℃ oxygen by pipeline 112.Further, in order to reclaim carbon, will supply to the gasification reaction operation 101 through pipeline 111 by pipeline 123 from the carbon oil (mixture of carbon and gasified raw material) that carbon recovery process 104 is drawn.
In the gasification reaction operation 101, at 1300～1400 ℃ of temperature, pressure 60～80Kg/cm
2Carry out partial oxidation reaction under the condition of-G.After the thick gas heat release of adopting this partial oxidation reaction to gasify is recycled to about 200～250 ℃, supply in the cooling carbon washing procedure 102 by pipeline 114.At this moment, the hydrogen sulfide content in the thick gas is more than prussic acid.For example, the volume ratio of hydrogen sulfide and prussic acid is preferably 10～40 times, more preferably 15～20 times.
In the cooling carbon washing procedure 102, in order to carry out de-carbon one time, the thick gas that has gasified in order to remove the carbon in the thick gas fully, is washed under about 40～50 ℃ in about 130～140 ℃ of washing and coolings down, is separated into thick gas and carbon slurry.Preferentially generate nickelous sulfide or other sulfide in this carbon slurry, and suppress the generation of nickel-cyano complex significantly.So, the carbon in the thick gas is removed in cooling carbon washing procedure 102 fully, and the thick gas that contains hydrogen sulfide etc. is supplied in the desulfurization process 103 by pipeline 115.
In the desulfurization process 103, with the saturated absorption liquid of carbonic acid gas sulphur compound is optionally absorbed and to remove.The gas of absorbing and removing also contains a large amount of carbonic acid gas from absorption liquid except hydrogen sulfide.Therefore, can in the enrichment process that is provided with as required, hydrogen sulfide be concentrated into about 20 weight %.The sour gas that has concentrated is discharged by pipeline 117, and is wherein most of as the sulphur source of supplying with gasification reaction operation 101, is recycled in the pipeline 111 by pipeline 118.Remaining sour gas can supply in the outer sulfur recovery process of system, also can handle with roasting kiln.The thick gas that removes sulphur in desulfurization process 103 is supplied in other treatment process by pipeline 116.
The carbon slurry that generates in the cooling carbon washing procedure 102, is supplied in the carbon recovery process 104 by pipeline 119 after normal pressure is returned in decompression owing to be in pressurized state.This carbon slurry also contains hydrogen sulfide (H except containing carbon
2S), ammonia (NH
3), prussic acid lysed gas and heavy metals such as nickelous sulfide and iron sulphide such as (HCN).
The part of heavy metal such as nickelous sulfide and iron sulphide composition and the carbon of recovery mix with the gasified raw material that pipeline 124 is supplied with and obtain flowability, are recycled in the gasification reaction operation 101 through pipeline 111 by pipeline 123.
In carbon recovery process 104, be recovered in the slurries that remove carbon etc., also be dissolved with heavy metal, NH such as residual nickelous sulfide, iron sulphide
3, HCN, H
2S, CO
2, CO, H
2Heavy metal compound such as nickelous sulfide, iron sulphide, in the precipitation operation in carbon recovery process 104, precipitated the removing of heavy metal of the about 80 weight % that contain in the gasified raw material.
Be discharged into by carbon recovery process 104 in the waste water of pipeline 120, be dissolved with heavy metal and the NH of about 20 weight % in the gasified raw material
3, HCN, H
2S, CO
2, CO, H
2This waste water is supplied in the cyanogen stripping operation 105, handle so that before the wastewater treatment operation is handled, dissolved gases is carried out stripping, at about 1.0～1.5Kg/cm with steam
2, under about 100～110 ℃ condition, mainly remove most HCN, NH
3, by pipeline 122 dischargings.
In cyanogen stripping operation 105, be removed the waste water of above-mentioned gas, mainly contain nickel, NH
3, the trace iron and HCN, supply to sewage treatment equipment by pipeline 121.With caustic soda the pH value is adjusted to 9.5～11 in chemical method wastewater treatment operation, nickel, iron are removed as nickel hydroxide and ironic hydroxide respectively.Simultaneously, contain small amount of H CN, NH
3Waste water handle with biological process wastewater treatment operation, finally be discharged into outside the system.
In addition, can also adopt following method of wastewater treatment in the cyanogen stripping operation 105.
Method of wastewater treatment of the present invention can be used for handling the waste water (hereinafter referred to as " cyanide wastewater ") that contains heavy metal ion (nickel ion, vanadium ion, iron ion etc.), cyanogen, ammonia, carbonic acid gas, hydrogen sulfide and nickel-cyano complex.But, method of wastewater treatment of the present invention is as the original processing object with the waste water that generates in the gasification process, said gasification is to contain hydrogen, carbon, nitrogen, sulphur and nickel, vanadium, the coal of heavy metals such as iron or mink cell focus, long residuum, vacuum residuum, refining of petroleum residual oil such as pitch are raw material, oxygen of supplying with air separation plant and the steam of supplying with from the outside at high temperature carry out, therefore, contain above-mentioned heavy metal ion, cyanogen, ammonia, carbonic acid gas, the waste water of the composition beyond hydrogen sulfide and the nickel-cyano complex also is applicable object of the present invention.
The prerequisite of method of wastewater treatment of the present invention is, when using 1 above stripping tower to carry out the stripping processing, the waste water ph of this occasion is adjusted to 2.0～6.0, as long as but satisfy this prerequisite, the technician constitutes the common change of making to other and is also included among the present invention.Below based on the embodiment of description of drawings method of wastewater treatment of the present invention.
Fig. 2 is for incorporating into the invention embodiment (1) of method of wastewater treatment and the process flow diagram of (2) in cyanogen stripping operation 105.Fig. 3 and Fig. 4 are the process flow diagram of invention embodiment (2), the implication that the symbolic representation identical with Fig. 2 is identical.
In more detail, Fig. 3 is the process flow diagram of 1 stripping tower of use that is used to illustrate an embodiment of method of wastewater treatment, and Fig. 4 is the process flow diagram of 2 stripping towers of use that is used to illustrate another embodiment of method of wastewater treatment.
An embodiment of method of wastewater treatment at first, is described based on Fig. 3.Among Fig. 3, the inside column plate section of stripping tower 201 is to be made of for 203 two sections upper tray section 202 and bottom column plate section.Stage number and column plate wait at interval that there is no particular limitation, can use the stripping tower of general structure.
Cyanide wastewater supplies to upper tray section 202 by the pipeline 210 that is connected with stripping tower 201.As an example of this waste water, can enumerate about 40～60 ℃ of the temperature that is produced when making the raw material that the hydrogen cyanide content that generates in the gasification process Duos than hydrogen sulfide, the waste water of pH value about 8.0～110.
Acid is supplied to the middle part of upper tray section 202 and bottom column plate section 203 by the pipeline 211 that is connected with stripping tower 201.Acid can be used strong acid such as hydrochloric acid, sulfuric acid.To the low too many temperature of temperature unlike cyanide wastewater, the temperature of cyanide wastewater is used about 15～50 ℃ acid in above-mentioned scope the time with the temperature regulation of acid in hope.
The feed rate of acid is the pH value of cyanide wastewater to be adjusted to 2.0～6.0, preferred 2.5～4.5 amount.By the pH value is adjusted in the above-mentioned scope, can at an easy rate nickel-cyano complex be resolved into nickel ion and cryanide ion.
Steam is supplied to the below of bottom column plate section 203 by the pipeline 212 that is connected with stripping tower 201.Can supply with for example about 120～200 ℃ of temperature, the about 2～11Kg/cm of pressure
2Steam.
So, in the stripping tower 201 of supplying with cyanide wastewater, acid and steam, mainly be that ammonia, hydrogen sulfide, carbonic acid gas etc. are separated from cyanide wastewater by stripping in the upper tray section 202.Nickel-the cyano complex that contains in the cyanide wastewater does not decompose in upper tray section 202, by the pH value is adjusted to 2.0～6.0, is broken down into free nickel ion (Ni in bottom column plate section 203
2+) and cryanide ion (CN
-).At this moment, the pressure of the pressure of upper tray section 202 and bottom column plate section 203 is preferably, and the pressure of upper tray section 202 is 1 o'clock, and the pressure of bottom column plate section 203 is 1.01～1.1.
The cryanide ion that generates in the bottom column plate section 203, in identical column plate section, pass through stripping, separate from waste water as prussic acid, rise in the upper tray section 202 of stripping tower 201, with ammonia, hydrogen sulfide, carbonic acid gas and the steam of the condition of high temperature, supply in the condenser 204 by the pipeline 213 that is connected with stripping tower 201.
Then, after the cooling, supplied in the separator 205 by pipeline 214 in condenser 204, water of condensation is sent back to the top of the upper tray section 202 of stripping tower 201 by pipeline 215.The prussic acid of separating with water of condensation in separator 205, ammonia, carbonic acid gas, hydrogen sulfide and a part of steam are discharged into outside the system by pipeline 216.
Simultaneously, the isolating hot wastewater that contains free nickel ion is discharged by pipeline 217 in the column plate section 203 of the bottom of stripping tower 201, handles in chemical method wastewater treatment operation.In this chemical method wastewater treatment operation, for example, the pH value is adjusted to 9.5～11 with caustic soda, free nickel ion is removed as nickel hydroxide.
Below, another embodiment of method of wastewater treatment is described based on Fig. 4.The treatment condition of the embodiment shown in Fig. 4 can be that benchmark is set with embodiment shown in Figure 3.That is, can similarly method of wastewater treatment shown in Figure 4 be combined in the cyanogen stripping operation 105 with Fig. 3.Among Fig. 4,2 stripping towers (the 1st stripping tower 300 and the 2nd stripping tower 310) are set, each is made of the inside of the 1st stripping tower 300 and the 2nd stripping tower 310 1 section column plate section 301,311.
Cyanide wastewater is supplied to the top of column plate section 301 by the pipeline 320 that is connected with the 1st stripping tower 300.
Acid connect the 1st stripping tower 300 below and the 2nd stripping tower 310 above hope position and the 1st stripping tower 300 of pipeline 325 below the cyanide wastewater of discharge mix, making the pH value is 2.0～6.0.Mix sour cyanide wastewater and supplied to the top of the column plate section 311 of the 2nd stripping tower 310.
Steam is supplied to the below of column plate section 311 by the pipeline 326 that is connected with the 2nd stripping tower 310.The steam of supplying with the 2nd stripping tower 310 also supplies to the below of the column plate section 301 of the 1st stripping tower 300 by pipeline 328.
So, in the 1st stripping tower 300 of supplying with cyanide wastewater, acid and steam, mainly adopt vaporizing extract process from waste water, to separate ammonia, hydrogen sulfide, carbonic acid gas.
By the pH value is adjusted into 2.0～6.0, the nickel-cyano complex that contains in the cyanide wastewater is broken down into free nickel ion (Ni in the 2nd stripping tower 310 column plate sections 311
2+) and cryanide ion (CN
-).Then, the cryanide ion that generates in the column plate section 311 by stripping, is separated from waste water as prussic acid in identical column plate section.Like this, in the 2nd stripping tower 310, can carry out the decomposition of nickel-cyano complex and separating of prussic acid simultaneously.
Prussic acid rises in the upper tray section 311 of the 2nd stripping tower 310, and by pipeline 328, the pipeline 321 by being connected with the 1st stripping tower 300 again supplies in the condenser 304 with ammonia, hydrogen sulfide, carbonic acid gas and the steam of the condition of high temperature.
Then, after the cooling, supplied in the separator 305 by pipeline 322 in condenser 304, water of condensation is sent back to the top of the column plate section 301 of the 1st stripping tower 300 by pipeline 323.In separator 305 with the isolating prussic acid of water of condensation, ammonia, carbonic acid gas, hydrogen sulfide and a part of steam by outside the pipeline 324 discharge systems.
Simultaneously, the isolating hot wastewater that contains free nickel ion is discharged by pipeline 327 in the column plate section 311 of the 2nd stripping tower 310, handles in chemical method wastewater treatment operation.
According to the present invention, the generation of the nickel-cyano complex in the waste water that produces in the time of can suppressing significantly to use the few gasified raw material of sulphur content to adopt the partial oxidation process gasification.Owing to can adopt vaporizing extract process in the past to handle waste water, so wastewater treatment becomes easily, and environment is not had detrimentally affect yet.
Further, according to the present invention, the nickel-cyano complex in the waste water that produces in the time of can adopting in the past vaporizing extract process will use the few material gasification of sulphur content decomposes, so wastewater treatment is become easily, and environment is not had detrimentally affect yet.
Embodiment
Below illustrate in greater detail the present invention with embodiment, but the present invention is not subjected to the qualification of these embodiment.
Embodiment 1
As gasified raw material, the vacuum residuum with following composition that uses refining of petroleum to obtain adopts technical process shown in Figure 1, handles as follows.
Component content
C 86.70 weight %
H 12.10 weight %
S 0.17 weight %
N 0.51 weight %
O 0.50 weight %
Ash content 0.02 weight %
Nickel 75.10 ppm by weight
Vanadium 0.90 ppm by weight
Iron 5.60 ppm by weight.
50 weight % flows of gasified raw material are supplied in the gasification reaction operation 101, be used to adopt the gasification of partial oxidation process, 50 weight % flows are supplied in the carbon recovery process 104.
Supply with about 400 ℃ steam by pipeline 112 to gasification reaction operation 101, supply with about 230 ℃ oxygen by pipeline 113.In addition, with the spissated H that contains in the desulfurization process 103
2The sour gas of S supplies in the gasification reaction operation 101 by the amount that is equivalent to 0.83kg concerning the 100kg gasified raw material.In addition, at start of run, will supply to the gasification reaction operation 101 from the outside with the sulphur of above-mentioned equal quantities.In the gasification reaction operation 101, at 1300～1400 ℃ of temperature, pressure 60～80Kg/cm
2Carry out partial oxidation reaction under the condition of-G.
In the ingress of gasification reaction operation 101, heavy metal is formed 3 times (weight) at the initial stage that is adjusted into, sulphur is formed be adjusted into 1 weight %.Each composition is shown in as follows.
Component content
C 86.07 weight %
H 11.88 weight %
S 1.00 weight %
N 0.51 weight %
O 0.49 weight %
Ash content 0.05 weight %
Nickel 225.30 ppm by weight
Vanadium 2.70 ppm by weight
Iron 16.80 ppm by weight.
After the thick gas heat release of having gasified in the gasification reaction operation 101 is recycled to about 200 ℃, supplies to cooling carbon by pipeline 114 and remove in the operation 102.Still contain the unreacted carbon that accounts for gasified raw material 1.0 weight % in the gas of gasification reaction operation 101 outlets.
Cooling carbon is removed in the operation 102, and thick gas washs down with after removing carbon elimination and being cooled to 45 ℃ at about 140 ℃, washes again.The consumption of washing water is that to make the carbon in the slurries be the amount of 1.0 weight %.Because washing water use the reuse water in the carbon recovery process 104, the heavy metal that wherein contains is about 1.1 times (weight) in the gasified raw material.Therefore, the heavy metal that contains in the carbon slurry is about the heavy metal of 4.1 times (weight), its be with gasified raw material from gasification reaction operation 101 in the heavy metal sum of about 3 times (weight).
The carbon slurry of cooling carbon washing procedure 102 dischargings is supplied in the carbon recovery process 104 by pipeline 119.Be enough to make nickel to generate the H of nickelous sulfide owing to contain in the carbon slurry
2S can preferentially generate nickelous sulfide etc.In the middle of the heavy metal that is equivalent to 4.1 times (weight) of heavy metal in the gasified raw material that contains in the carbon slurry, the heavy metal that is equivalent to 2.0 times (weight) is recycled in the gasification reaction operation 101 by pipeline 123 with the state that is present in the carbon oil cycling stream.
The carbon oil cycling stream is 50 weight % of gasified raw material, and actual heavy metal concentration is concentrated into 5 times (weight).Therefore, with respect to gasified raw material, remove the heavy metal that contains 2.1 times (weight) in the washing water that utilize again behind the carbon elimination.
The waste water that contains the heavy metal of the heavy metal 1.3 times (weight) that is equivalent in the gasified raw material wherein contains the steam that supplies in the gasification reaction operation 101 and reacts the unnecessary water that generates, and handles in cyanogen stripping operation 105 and wastewater treatment operation.As washing water, the water of cycling and reutilization is 110: 20 with the weight ratio that supplies to the water of cyanogen stripping operation 105.Supply to the 20 weight % that contain the heavy metal in the gasified raw material in the waste water of cyanogen stripping operation 105, its form is nickelous sulfide and iron sulphide.
Residual heavy metal precipitates and isolates 80 weight % with the settlement separate equipment in the carbon recovery process 104, after handling in cyanogen stripping operation 105, handles the heavy metal of all the other 20 weight % in the wastewater treatment operation.Because heavy metal supplies to respectively in the cyanogen stripping operation 105, at 1.5Kg/cm with the form of HCN with form, the cyanogen of nickelous sulfide and iron sulphide
2, be easy to decompose under the about 110 ℃ condition, can be used as H
2S, HCN stripping separate.By steam stripped gas composition is NH
383 volume %, CO
212 volume %,
HCO, the H of 2S 2.5 volume %, HCN 2.5 volume % and trace
2, can burn as auxiliary fuel or with flare as required.
Supply with in the waste water of wastewater treatment operation, mainly contain nickel 15 ppm by weight, NH
3The iron and the HCN of 250 ppm by weight, trace, but can handle fully with interior at the prescribed value of wastewater treatment operation.
Comparative example 1
Use gasified raw material similarly to Example 1,, handle by embodiment 1 by technical process shown in Figure 1.But, do not make the H that contains from desulfurization process 103
2The sour gas of S circulates, and therefore, during the gasified raw material of gasification reaction operation 101 ingress was formed, heavy metal was 7.2 times (weight), and sulphur is 0.17 weight %.Each composition is shown in as follows.
Component content
C 86.72 weight %
H 11.975 weight %
S 0.17 weight %
N 0.50 weight %
O 0.495 weight %
Ash content 0.14 weight %
Nickel 540.70 ppm by weight
Vanadium 2.70 ppm by weight
Iron 16.80 ppm by weight.
Contain the unreacted carbon that accounts for gasified raw material 1.0 weight % in the exit gas of gasification reaction operation 101.
In the cooling carbon washing procedure 102, the consumption of washing water is that to make the carbon in the carbon slurry be the amount of 1.0 weight %.Because washing water use the reuse water in the carbon recovery process 104, therefore wherein contain about 5.5 times (weight) of heavy metal in the gasified raw material.Therefore, the heavy metal that contains in the slurries, for gasified raw material from gasification reaction operation 101 in the heavy metal sum of about 7.2 times (weight), be the heavy metal of about 12.7 times (weight).In the slurries that cooling carbon washing procedure 102 is discharged, the H that contains
2Therefore the S deficiency preferentially generates nickel-cyano complex so that nickel generates nickelous sulfide.
Be equivalent in the slurries in the middle of the heavy metal of 12.7 times (weight), the heavy metal that is equivalent to 6.2 times (weight) is present in the carbon oil cycling stream, is recycled in the gasification reaction operation 101.The carbon oil cycling stream is 50 weight % of gasified raw material, and actual heavy metal concentration is concentrated into 13.4 times.
Remove the heavy metal that contains heavy metal 6.6 times of weight that are equivalent in the gasified raw material in the washing water that carbon elimination utilizes again, because the nickel in the gasified raw material generates highly stable nickel-cyano complex [Ni (CO) in alkaline range
4]
2-, therefore can not precipitate and separate in carbon recovery process 104.
Contain the waste water that is equivalent to the heavy metal of heavy metal 6.6 times of weight in the gasified raw material, wherein contain the steam of supplying with gasification reaction operation 101 and react the unnecessary water that generates, in cyanogen stripping operation 105 and wastewater treatment operation, handle.As the water of washing water cycling and reutilization and the ratio of the water of supplying with cyanogen stripping operation 105 is 550: 100.
Supply with in the waste water of cyanogen stripping operation 105, contain the heavy metal of the heavy metal 100 weight % in the gasified raw material, its form is nickel-cyano complex and iron sulphide.Because heavy metal is supplied with cyanogen stripping operation 105 with form, the cyanogen of nickel-cyano complex and iron sulphide respectively with the form of nickel-cyano complex, therefore, in alkaline range, at 1.5Kg/cm
2, can not separate fully under the about 110 ℃ condition and remove.
Remaining heavy metal is handled in the wastewater treatment operation after handling in cyanogen stripping operation 105 all.Supply with in the treating water of wastewater treatment operation, mainly contain nickel-cyano complex 75 ppm by weight (by nickel), NH
3The iron of 250 ppm by weight and trace, it is all very difficult to carry out chemical treatment and this processing of two kinds of biological treatment in the wastewater treatment operation.
Embodiment 2
More preferably, in cyanogen stripping operation 105, can adopt following method of wastewater treatment.
Below with Fig. 3 method of wastewater treatment is described.
As raw material, the vacuum residuum with following composition that uses refining of petroleum to obtain adopts partial oxidation process that it is gasified, by the technical process shown in Fig. 3, and the waste water (cyanide wastewater) that produces when handling gasification as follows.
Component content
C 86.70 weight %
H 12.10 weight %
S 0.17 weight %
N 0.51 weight %
O 0.50 weight %
Ash content 0.02 weight %
Nickel 75.10 ppm by weight
Vanadium 0.90 ppm by weight
Iron 5.60 ppm by weight.
About 8000 L/H of the cyanide wastewater of 60 ℃ of temperature, pH9.79 are supplied to the top of the upper tray section 202 of stripping tower 201 by pipeline 210.Then, when supplying with cyanide wastewater, between the upper tray section 202 of stripping tower 201 and bottom column plate section 203, supply with the sulfuric acid (20 ℃) that is used to adjust the pH value by pipeline 211.Adjust feed rate, so that the pH value of the cyanide wastewater of column plate section 203 belows, bottom of stripping tower 201 is 4.13.Further, steam (180 ℃ of temperature, pressure 4.5Kg/cm
2) supply to the below of the bottom column plate section 203 of stripping tower 201 by pipeline 212 with 1.9 tons/hour ratios.At this moment, regulate the pressure of upper tray section 202, so that the pressure of bottom column plate section 203 reaches 1.5g/kgcm
2, turn round.
After turning round about 24 hours, the gaseous mixture (107 ℃ of temperature) that contains prussic acid, ammonia, hydrogen sulfide, carbonic acid gas and a part of steam is cooled to 90 ℃ in condenser 204 after, through separator 205, outside pipeline 216 discharge systems.In addition, isolating 110 ℃ the hot wastewater that contains free nickel ion is discharged by pipeline 217 in the column plate section 203 of the bottom of stripping tower 201.Measure the waste water composition of discharging like this.The results are shown in the table 1.
Comparative example 2
Use with embodiment 2 and form identical cyanide wastewater, handle with stripping tower shown in Figure 3 201.But the column plate section is 1 section (sum of column plate section is identical with embodiment 2), does not supply with acid.Measure the waste water composition after handling.The results are shown in the table 1.
Table 1
Nickel-cyano complex is decomposed, and exists hardly in waste water.
| Embodiment 2 | Comparative example 2 | ||
| Waste water composition before handling | |||
| Nickel (ppm by weight) | ????80.4 | ????80.4 | |
| Cyanogen (ppm by weight) | ????164.5 | ????164.5 | |
| ????pH | ????9.79 | ????9.79 | |
| Waste water composition after the processing | |||
| Cyanic acid nickel ion (ppm by weight) | Can not detect | ????151.5 | |
| Free nickel ion (ppm by weight) | ????65.0 | ????9.6 | |
| Cyanogen (ppm by weight) | ????0.5 | ????106.8 | |
| Nickel composition partition ratio (%) | The cyanic acid nickel ion | Can not detect | ????85.3 |
| Free nickel ion | ????100.0 | ????14.7 | |
| ????pH | ????4.13 | ????6.31 | |
Claims (9)
1. gasification process, it is that the vaporized raw material of wanting that will contain the sulphur of the nickel of 10～100 ppm by weight and 0.1～1.0 weight % adopts partial oxidation process carry out gasification process, through overcooling, carbon washing, desulfurization, obtains the method for thick gas resultant, it is characterized in that
From the waste water of washing procedure, reclaim carbon,
(1) sulphur is mixed into wants in the vaporized raw material, its consumption is to make the hydrogen sulfide content that generates in the gasification process more than prussic acid, and waste water is carried out the cyanogen stripping handle, perhaps
(2) waste water that will contain the washing procedure of nickel-cyano complex carries out stripping when handling in 1 above stripping tower, in stripping tower, supply with acid, so that the pH value of waste water is adjusted to 2.0～6.0, thus nickel-cyano complex is resolved into nickel ion and cryanide ion, nickel ion is processed as nickel hydroxide, and cryanide ion is processed as prussic acid.
2. the method described in the claim 1 wherein, vaporized raw material be heavy oil, long residuum, vacuum residuum or the pitch that coal or refining of petroleum obtain.
3. the method described in the claim 1 is comprising (1).
4. the method described in the claim 3, wherein, sulphur content is 0.5～2.0 weight %.
5. the method described in the claim 3, wherein, the sulphur that is mixed in the raw material is to concentrate hydrogen sulfide containing sour gas of removing or the sulfur-bearing thing of supplying with from the outside in the desulfurization process.
6. the method described in the claim 1 is comprising (2).
7. the method described in the claim 6 wherein, when handling in 1 stripping tower, uses inner column plate section by upper tray section and two sections stripping towers that constitute of bottom column plate section, supplies with waste water to the upper tray section, supplies with acid to bottom column plate section.
8. the method described in the claim 6, wherein, when in 2 above stripping towers, handling, the column plate section of each stripping tower inside constitutes by 1 section, supply with waste water from the column plate section top of the 1st stripping tower, mixing acid in the waste water that discharge the 1st stripping tower below supplies to above the column plate section of the 2nd stripping tower then.
9. the method described in the claim 1 wherein, is recovered to the carbon that has washed in the gasification process.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11641198 | 1998-04-27 | ||
| JP116411/1998 | 1998-04-27 | ||
| JP11641098A JPH11302667A (en) | 1998-04-27 | 1998-04-27 | Gasification process |
| JP116410/1998 | 1998-04-27 | ||
| JP10143822A JP2000015249A (en) | 1998-04-27 | 1998-05-26 | Treatment of waste water |
| JP143822/1998 | 1998-05-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1307626A true CN1307626A (en) | 2001-08-08 |
Family
ID=27313150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99807937 Pending CN1307626A (en) | 1998-04-27 | 1999-04-20 | Gasification method |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1307626A (en) |
| DE (1) | DE19983179T1 (en) |
| WO (1) | WO1999055804A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106661469A (en) * | 2014-06-28 | 2017-05-10 | 沙特阿拉伯石油公司 | Energy efficient gasification based multi generation apparatus employing energy efficient gasification plant-directed process schemes and related methods |
| CN113045045A (en) * | 2021-03-26 | 2021-06-29 | 长春黄金研究院有限公司 | Complete device and method for treating acidified cyanide-containing wastewater by using atomized gas normal-temperature condensation method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948210B (en) * | 2010-09-14 | 2012-07-04 | 湖州德翔环境科技有限公司 | Treating process of navajoite waste water |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2733105B1 (en) * | 1977-07-22 | 1979-01-18 | Basf Ag | Process for the production of synthesis gases by partial oxidation |
| CN86104274A (en) * | 1985-06-26 | 1987-05-13 | 国际壳牌研究公司 | Remove prussic acid, ammonia and carbon oxysulfide in the synthetic gas |
-
1999
- 1999-04-20 CN CN 99807937 patent/CN1307626A/en active Pending
- 1999-04-20 WO PCT/JP1999/002099 patent/WO1999055804A1/en active Application Filing
- 1999-04-20 DE DE19983179T patent/DE19983179T1/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106661469A (en) * | 2014-06-28 | 2017-05-10 | 沙特阿拉伯石油公司 | Energy efficient gasification based multi generation apparatus employing energy efficient gasification plant-directed process schemes and related methods |
| CN106661469B (en) * | 2014-06-28 | 2019-12-17 | 沙特阿拉伯石油公司 | Energy efficient gasification-based polygeneration apparatus employing energy efficient gasification plant-related process schemes and related methods |
| CN113045045A (en) * | 2021-03-26 | 2021-06-29 | 长春黄金研究院有限公司 | Complete device and method for treating acidified cyanide-containing wastewater by using atomized gas normal-temperature condensation method |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1999055804A1 (en) | 1999-11-04 |
| DE19983179T1 (en) | 2001-05-17 |
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