CN101234753A - Method and apparatus for recovering sulfide and protein from depilation waste liquor - Google Patents
Method and apparatus for recovering sulfide and protein from depilation waste liquor Download PDFInfo
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- CN101234753A CN101234753A CNA2007100634971A CN200710063497A CN101234753A CN 101234753 A CN101234753 A CN 101234753A CN A2007100634971 A CNA2007100634971 A CN A2007100634971A CN 200710063497 A CN200710063497 A CN 200710063497A CN 101234753 A CN101234753 A CN 101234753A
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Abstract
The invention discloses a method used for recycling sulfide and protein from leather unhairing waste liquid and a device. The device presses acid solution into the unhairing waste liquid of a sealing reactor and stirs the unhairing waste liquid by using compressing gas; the generated hydrogen sulfide gas is taken out from the sealing reactor by using air stream generated from the compressing gas, and hydrogen sulfide gas is absorbed by alkaline solution; sulfide which can be used for unhairing process is regenerated, meanwhile, the PH value of the unhairing waste liquid is adjusted to near an isoelectric point of the protein to precipitate the protein; the processed unhairing waste liquid is pressed out by using the compressing gas; the generated protein precipitate is separated and recycled. The invention also discloses a device specially used for carrying out the method of the invention. The device has the advantages of simple structure, no use of metal material, low investment of equipment and big capacity. As the method of the invention uses air stream to bring the hydrogen sulfide gas out of the reactor, the recycling rate of the sulfide is much higher than common methods.
Description
The method field
The invention belongs to the technology that cleans of leather production technical field, specially refer to a kind of sulfide and method of protein and device of from the depilation waste liquor that tanning production produced, reclaiming.
Background method
The pollution of leather industry mainly comes from prepares workshop section, and the pollution of preparing workshop section mainly comes from the depilation operation, in the pollution that leather production produces except sulphide staining fully from the sulfide depilation operation, also has the pervaporation residue more than 65%, organism more than 61%, total nitrogen more than 40% and 70% above chemical oxygen demand (COD
Cr) also from the depilation operation.
In occupation of absolute dominant position, reason is that the sulfide depilation method has the unrivaled advantage of other epilation to the sulfide depilation method in the depilating method that current leather is produced: 1. depilation is clean and speed is fast; 2. the material that loses hair or feathers obtains easily and is with low cost; 3. easy, the easy control of epilation operation can realize protecting the hair depilation or ruin the hair depilation; 4. good product quality and more stable, the leather kind that is suitable for is wide.
But also there is heavy-polluted fatal shortcoming in the sulfide depilation method simultaneously, and it pollutes pollution and the organic pollution that mainly comprises sulfide.Sulfide residual in the depilation waste liquor can cause severe contamination to environment, the waste water of sulfur compound enters can make the smelly blackening of water quality in the rivers, many fresh-water fishes sulfide content be in the water of 1.0-25mg/l 1-3 days will be dead, containing a large amount of sulfide in the soil can make the old root blackout of plant rot, new root is long bad, causes farm crop withered.Another the most serious harm of sulfide, be exactly that it can be converted into the stronger hydrogen sulfide of toxicity, hydrogen sulfide has the intense stimulus effect to eyes and respiratory tract, be subjected to low concentration hydrogen sulphide effect meeting to make people's dizziness, general weakness, easily tired, hidrosis for a long time, pleasantly sweet in mouthful, feel sick, concentration of hydrogen sulfide Gao Shihui make people's dim eyesight, dizzy until lose consciousness, death.When airborne concentration of hydrogen sulfide reaches 0.015mg/l, will cause toxicity symptom, concentration then can cause death when surpassing 1mg/l.Processing to sulfur compound sewage is expensive very big in addition, and the energy of its consumption is three times of no sulphur sewage except that equipment, and if sulfide content surpasses 50mg/l in the sewage, sludge bacteria can be died, and has reduced water treatment effect.
Hair on the process hides raw material skin and epidermis will be removed by chemical process in the depilation operation, these main components be the process hides dud of keratoprotein account for raw material skin dry weight 5～10%, in the depilation operation, after degrading, all enter in the depilation waste liquor basically, become the principal pollutant of leather-making waste water.In addition, the most of interfibrillar substance in the process hides raw material skin also will be removed by the depilation operation, and the main component of interfibrillar substance is some ball-type albumen, and this has also improved the organic content in the depilation waste liquor to a certain extent greatly.A large amount of protein in the depilation waste liquor make it become greatest contamination source in the leather-making waste water, COD
CrContent is up to more than the 20000mg/l, and general chemical oxygen demand can make the microorganism in the water when 500-3000mg/l, comprises that disease carrying germ obtains enough nutrition and breeding rapidly, causes pollution of waterhead, is detrimental to health.When containing large amount of organic in the water in addition, the dissolved oxygen in the water is consumed in a large number, when oxygen in water less than 4 the time, hydrocoles such as the fish expiratory dyspnea that can become gradually, so be choked to death and die.
In order to improve the with serious pollution shortcoming of sulfide depilation method, the scientific worker has developed some depilating methods that clean both at home and abroad, comprise the depilating method that does not use sulfide, as organosulfur epilation, oxidation style depilation, organic amine epilation and enzyme unhairing etc., or original depilating method improved to reduce the pollution of sulfide depilation method, as few sulphur epilation and Bao Mao epilation etc.Although the scientific worker has developed the various depilation novel methods that clean both at home and abroad, but these methods all are not applied basically aborning, major cause be original dehairing process is changed excessive, thereby the shortcoming of following five aspects of ubiquity: 1. complicated operation, be difficult to control; 2. lose hair or feathers cost than higher; 3. it is more limited to clean effect; 4. equipment there is particular requirement; 5. influential to quality product.
Contain a large amount of residual sulfide in the depilation waste liquor that tanning production produces, can carry out recycle in epilation process, the depilation waste liquor circulation method comprises direct circulation method and abnormal circulation method.Directly circulation method is that direct reuse is in the depilation operation after depilation waste liquor being reclaimed and replenishes the depilation material, and the shortcoming of this method is that the salt and the protein content of depilatory solution in circulation constantly increases, thereby makes the process stabilizing performance poor, the quality product susceptible to.Abnormal circulation method is to use acid that the sulfide in the depilation waste liquor is transformed into hydrogen sulfide, stink damp body and function alkali absorbs the back and generates sulfide, be used further to the operation of losing hair or feathers, the advantage of this method is the sulfide purity height that reclaims, being back to production can not impact quality product, and when reclaiming sulfide, can reclaim protein, can reduce organic pollution significantly.
Generally all be to use reactor from depilation waste liquor, to reclaim sulfide and protein at present, earlier depilation waste liquor is added in the reactor, again the airtight back of reactor is being kept under the lasting condition of stirring, add acid solution after the dilution gradually by header tank, the hydrogen sulfide that the produces back of overflowing absorbs with alkali and regenerates sodium sulphite, again the protein that is precipitated out of Separation and Recovery.Mainly there is the shortcoming of the following aspects in this method:
1. have the sealing between stirring rake and the kettle in the reactor, the potentially dangerous that exists hypertoxic hydrogen sulfide to overflow, and stink damp cognition corrosion all metals except that gold, platinum can cause serious harm to conversion unit;
2. the stink damp volume density is 1.539, be heavier than air, can accumulate in lower, thereby the hydrogen sulfide that produces in the reactor can not be discharged fully, the rate of recovery of sulfide is lower, and the safety that residual stink damp is known from experience operator in the reactor works the mischief;
3. the amount of depilation waste liquor is bigger, and the tannery of general scale all can produce up to a hundred tons waste liquid every day, and the volume of reactor is less and cost is higher, thereby can increase considerably the investment of equipment.
Owing to there is above shortcoming, relatively difficulty and cost are difficult in the actual production and apply than higher to reclaim sulfide and protein from depilation waste liquor
Summary of the invention
The objective of the invention is at the shortcoming that generally from the process hides depilation waste liquor, reclaims sulfide and protein method, a kind of easy to operate, safe novel method is provided, and provide a kind of simple in structure, facility investment is very low reclaims sulfide and recovery of protein device from depilation waste liquor.
Contain a large amount of sodium sulphite and protein in the depilation waste liquor that tanning production produces, make sodium sulphite in the depilation waste liquor be converted into hydrogen sulfide to discharge by adding acid, absorb with alkali again and regenerate the very high sodium sulfide solution of purity that can be used to lose hair or feathers, the pH value of controlling simultaneously in the depilation waste liquor makes it deposit out to isoelectric point of protein, by filtering or centrifugation, obtain and to carry out purifying as the protein of feedstuff protein or fertilizer after maybe the protein that reclaims can being dissolved again.
The reaction process that the inventive method relates to is as follows:
The recovery of sodium sulphite:
(in the depilation waste liquor) S
2-+ 2H
+→ H
2S ↑
H
2S+2OH
-→ S
2-(in the fresh solution)+2H
2O
Recovery of protein (P represents protein):
(in the depilation waste liquor)
+NH
3-P-COO
-+ H
+→
+NH
3-P-COOH ↓
+NH
3-P-COOH+OH
-→
+NH
3-P-COO
-(in the fresh solution)+H
2O
Can the sulfide in the depilation waste liquor be converted into the pH value that hydrogen sulfide depends primarily on solution, and the sulfide concentration in the solution.
By accompanying drawing 1 as can be seen, when the sulfonium ion concentration ratio was higher in the solution, sulfonium ion just can be converted into hydrogen sulfide and discharges under the slight alkalinity condition, when pH value of solution less than 5 the time, sulfonium ions all in the solution all transform into hydrogen sulfide.
Isoelectric point of protein is generally between 3.5～4.5 in the depilation waste liquor, in the time of near the pH of protein soln reaches iso-electric point, positive changes on the protein molecule and negative charge number are more approaching, net charge number on the protein molecule is minimum, minimum with protein molecule with suction type bonded water molecules, thereby also reach minimum the water-soluble of this pH scope internal protein, thus can make proteins deposited come out in the depilation waste liquor, reach isolating purpose.
Isoelectric point of protein in acid range be because the amount of the acidic-group (mainly being carboxyl) on the protein greater than the amount of basic group (mainly be amino), after adding acid, the part acidic-group is closed, make charged basic group number and acidic-group number approaching, proteinic solubleness reduces and deposits.Reclaim required pH value scope because proteinic deposition pH scope between 3.5～4.5, just in time satisfies sodium sulphite, reclaim protein and can carry out simultaneously with recovery sodium sulphite.
Method provided by the invention does not adopt the stirring action of stirring rake in the reactor when reclaiming sulfide and protein from depilation waste liquor, but adopt the method that the feeding pressurized gas seethes waste liquid in depilation waste liquor that waste liquid is stirred, thereby can avoid the sealing problem of stirring rake, thereby container also can all adopt other material, as plastics and concrete structure etc., thereby avoid the use of metallic substance, prevent the corrosion of hydrogen sulfide equipment.
The advantage of method provided by the invention is to use pressurized gas that reaction system is stirred, make the sulfide reaction in acid and the depilation waste liquor produce hydrogen sulfide, and the hydrogen sulfide that utilizes air-flow to react to produce is taken container out of and is reclaimed, the acid that is added simultaneously makes the pH value of depilation waste liquor adjust to 2～6, preferred 3～5, more preferably 3.5～4.5, protein precipitation is come out and reclaim.
The required acid solution of reaction can be pressed in the encloses container by pressurized gas in the inventive method, thereby avoids the use of header tank.The air-flow that pressurized gas produced that feeds can be taken the hydrogen sulfide that produces in the encloses container out of, reacts with alkaline solution and is absorbed and regenerates sulfide.
Using pressurized gas to reclaim being also advantageous in that of hydrogen sulfide in the inventive method can thoroughly discharge the hydrogen sulfide that produces by time expand, and pressurized gas can also blow out the hydrogen sulfide that is dissolved in the water, increases substantially the rate of recovery of sulfide.
Reclaim containing the protein precipitation waste liquid and can discharge encloses container by discharge nozzle behind the sulfide in the inventive method by the pressure of gas, do not need discharge port to be set at container bottom, thereby this encloses container can be built in undergroundly, save construction investment, and can improve safety performance.
Provided by the inventionly from depilation waste liquor, reclaim sulfide and proteinic device comprises an airtight reaction vessel at least, this reaction vessel has at least a reaction vessel inlet pipe (1), band reaction vessel vapor pipe (2) of valve and one to be with the advancing of valve/discharge nozzle (5) to communicate with the external world, reaction vessel inlet pipe (1) with advance/mouth of pipe that discharge nozzle (5) links to each other with reaction vessel is positioned at the bottom of encloses container, the mouth of pipe that reaction vessel vapor pipe (2) links to each other with reaction vessel is positioned at the top of encloses container.In use earlier by advance/discharge nozzle (5) joins depilation waste liquor in the reaction vessel, close again into/discharge nozzle (5), acid solution after will diluting by pressurized gas is pressed in the closed reaction vessel, and the lasting pressurized gas that feeds stirs depilation waste liquor, simultaneously the hydrogen sulfide that produces is taken out of by reaction vessel vapor pipe (2), and absorbed the sulfide that generation can reuse with alkaline solution.Consumption by the control acid solution is adjusted to the pH value of depilation waste liquor near the isoelectric point of protein, protein precipitation in the depilation waste liquor is come out, treat to open into/discharge nozzle (5) after hydrogen sulfide reclaims fully, off-response vessel exhaust pipe (2), depilation waste liquor after utilizing the air pressure of pressurized gas to handle is discharged, and reclaims the protein precipitation of generation by centrifugation or filtering method again.
Provided by the inventionly from depilation waste liquor, reclaim sulfide and proteinic device can comprise that adds a sour container, this container can be designed as have a band valve add sour container inlet pipe (3), a band valve adds the encloses container of a sour container vapor pipe (4) and a lid that can seal (6), add the top that the mouth of pipe that sour container inlet pipe (3) links to each other with this container is positioned at container, add the bottom that the mouth of pipe that sour container vapor pipe (4) links to each other with this container is positioned at container, add sour container vapor pipe (4) the other end and link to each other with the inlet mouth 1 of closed reaction vessel.Close earlier during use and add sour container inlet pipe (3) and add sour container vapor pipe (4) valve, uncap (6), the acid solution that adds institute's expense, cover lid is opened and is added sour container inlet pipe (3) and add sour container vapor pipe (4) valve again, to adding sour container inlet pipe (3) feeding pressurized gas acid solution is pressed in the reaction vessel, and the lasting pressurized gas that feeds drains up to the hydrogen sulfide that produces.
Provided by the inventionly add adding sour container vapor pipe (4) and can link to each other in the sour container with the reaction vessel inlet pipe (1) of reaction vessel, can directly not be connected with the reaction vessel body by reaction vessel inlet pipe (1) yet, directly the advantage that links to each other is to control easily by by-pass valve control the add-on of acid solution, can not influence pressurized gas to the stirring of depilation waste liquor with take the hydrogen sulfide of generation out of.After adding the adding shortcoming that sour container vapor pipe (4) links to each other with the reaction vessel inlet pipe (1) of reaction vessel and be all must will add acid solution in the sour container at every turn and all be pressed into reaction vessel of sour container, could continue the feeding pressurized gas again to keep the stirring of waste liquid in the reaction vessel and to take the hydrogen sulfide of generation out of.
Provided by the inventionly from depilation waste liquor, reclaim the absorption unit that sulfide and proteinic device can comprise a hydrogen sulfide, this device can be designed to two continuous encloses containers, the basic solution that is used for absorbing hydrogen sulphide gas is housed in the container, the hydrogen sulfide of discharging from reaction vessel enters in the basic solution and generates sulfide with alkali reaction, after coming out from basic solution, unreacted hydrogen sulfide enters in the basic solution in another container, proceed reaction, absorb fully and do not contain hydrogen sulfide in the expellant gas of back, can directly enter in the atmosphere.The device of absorbing hydrogen sulphide gas also can use general absorption tower, and absorption liquid adopts basic solution.
Particular content of the present invention is as follows:
1, a kind of sulfide and method of protein of from the depilation waste liquor that tanning production produced, reclaiming, it is characterized in that depilation waste liquor is added in the closed reaction vessel, add acid, and the feeding pressurized gas stirs reaction system, make the sulfide reaction in acid and the depilation waste liquor produce hydrogen sulfide, and the air-flow that utilizes pressurized gas the to produce hydrogen sulfide that will react generation is taken reaction vessel out of and is reclaimed, the acid that is added simultaneously makes the pH value of depilation waste liquor adjust to 2～6, preferred 3～5, more preferably 3.5～4.5, protein precipitation is come out and reclaim.
2, a kind of device that is exclusively used in the 1 described method of enforcement, it is characterized in that this device comprises a closed reaction vessel at least, one adds sour container and an absorption unit, described closed reaction vessel has a reaction vessel inlet pipe 1 at least, advancing/discharge nozzle 5 of the reaction vessel vapor pipe 2 of a band valve and a band valve, reaction vessel inlet pipe 1 and advancing/discharge nozzle 5 is positioned at the bottom of closed reaction vessel, reaction vessel vapor pipe 2 is positioned at the top of closed reaction vessel, reaction vessel inlet pipe 1 with add sour container and communicate, reaction vessel vapor pipe 2 communicates with absorption unit or communicates with pressurized gas, advance/discharge nozzle 5 communicates with the external world.
3, according to 2 described devices, it is characterized in that described add sour container have at least a band valve add sour container inlet pipe 3, a band valve add that sour container vapor pipe 4 and one can seal add sour container lid 6, add sour container inlet pipe 3 one ends and be positioned at the top that adds sour container, the other end communicates with pressurized gas, add sour container vapor pipe 4 one ends and be positioned at the bottom that adds sour container, the other end links to each other with described reaction vessel inlet pipe 1, or directly communicates with the reaction vessel body.
4,, it is characterized in that described absorption unit is container or the conventional absorption tower that basic solution is housed according to 2 or 3 described devices.
5, according to 4 described devices, the concentration that it is characterized in that described basic solution is 0.1wt%～50wt%, preferred 1wt%～10wt%, used alkali is one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide, ammoniacal liquor, yellow soda ash and the sodium sulphite.
6, a kind of by from the depilation waste liquor that tanning production produced, reclaiming sulfide and method of protein as device as described in 4, it is characterized in that may further comprise the steps:
The vapor pipe (4) that 1. will add sour container links to each other with reaction vessel inlet pipe (1), and reaction vessel vapor pipe (2) links to each other with absorption unit;
2. open the valve of the advancing of closed reaction vessel/discharge nozzle 5, with depilation waste liquor by advance/discharge nozzle 5 is incorporated in this reaction vessel, close then into/valve of discharge nozzle 5;
3. open and add sour container lid 6, acid solution after diluting 1～10 times is joined in the sour container, cover tight lid 6, utilize pressurized gas with acid solution by adding during sour container vapor pipe 4 is pressed in the closed reaction vessel that depilation waste liquor is housed, and the lasting pressurized gas that feeds stirs the reaction system in the closed reaction vessel, take the hydrogen sulfide that the reaction of the sulfide in acid and the depilation waste liquor is produced out of reaction vessel by reaction vessel vapor pipe 2 by the air-flow that pressurized gas produces, and, obtain the sulfide that can utilize again with the absorption of the basic solution in the absorption unit;
4. control the above-mentioned acid solution amount that adds, make the pH value of depilation waste liquor reach 2～6, preferred 3～5, more preferably 3.5～4.5, the protein precipitation in the depilation waste liquor is come out; 5. after treating that hydrogen sulfide in the encloses container drains, open into/valve of discharge nozzle 5, the valve of off-response vessel exhaust pipe 2, depilation waste liquor after utilizing pressurized gas to produce air pressure will to handle by advance/discharge nozzle 5 extrudes encloses containers, again by the protein that filters or the centrifugation recovery is precipitated out.
7, a kind of by from the depilation waste liquor that tanning production produced, reclaiming sulfide and method of protein as device as described in 4, it is characterized in that may further comprise the steps:
The vapor pipe 4 that 1. will add sour container directly communicates with the reaction vessel body, and reaction vessel inlet pipe 1 links to each other with pressurized gas, and reaction vessel vapor pipe 2 links to each other with absorption unit;
2. open the valve of the advancing of closed reaction vessel/discharge nozzle 5, with depilation waste liquor by advance/discharge nozzle 5 is incorporated in this reaction vessel, close then into/valve of discharge nozzle 5;
3. open and add sour container lid 6, acid solution after diluting 1～10 times is joined in the sour container, cover tight lid 6, utilize pressurized gas with acid solution by add sour container vapor pipe 4 be pressed in the closed reaction vessel that depilation waste liquor is housed in closes compression gas then, continuing to feed pressurized gas by reaction vessel inlet pipe 1 simultaneously stirs the reaction system in the closed reaction vessel, take the hydrogen sulfide that the reaction of the sulfide in acid and the depilation waste liquor is produced out of reaction vessel by reaction vessel vapor pipe 2 by the air-flow that pressurized gas produces, and, obtain the sulfide that can utilize again with the absorption of the basic solution in the absorption unit;
4. control the above-mentioned acid solution amount that adds, make the pH value of depilation waste liquor reach 2～6, the protein precipitation in the depilation waste liquor is come out;
5. after treating that hydrogen sulfide in the encloses container drains, open into/valve of discharge nozzle 5, the valve of off-response vessel exhaust pipe 2, depilation waste liquor after utilizing pressurized gas to produce air pressure will to handle by advance/discharge nozzle 5 extrudes encloses containers, again by the protein that filters or the centrifugation recovery is precipitated out.
8,, it is characterized in that described acid is one or more in sulfuric acid, hydrochloric acid, nitric acid, formic acid, acetic acid and the phosphoric acid according to 1,6 and 7 any one described method.
9, according to 6 or 7 described methods, the concentration that it is characterized in that described basic solution is 0.1wt%～50wt%, preferred 1wt%～10wt%, used alkali is one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide, ammoniacal liquor, yellow soda ash and the sodium sulphite.
10 according to 1,6 and 7 any one described method, it is characterized in that the pressure of described pressurized gas is 0.001MPa～1MPa, is preferably 0.01MPa～0.5MPa, more preferably 0.05MPa～0.2MPa.
Apparatus and method of the present invention have the advantage of the following aspects:
1. can conveniently reclaim sulfide and protein in the process hides depilation waste liquor, eliminate the sulphide staining in the waste liquid and reduce Organic pollutants in the waste liquid significantly, the sulfide that reclaims can direct reuse in process hides depilation operation, the protein of recovery can as fertilizer or through behind the purifying as animal-feed albumen;
2. this device uses the stirring action of pressurized gas to replace the stirring action of stirring rake, thereby makes retrieving arrangement simple in structure, easy to operate, and safe and reliable;
3. this device can not use metallic substance, and can be built in subsurface, and facility investment is low, capacity is big, and potential hazardness is little;
4. this method uses air-flow to take the hydrogen sulfide that produces out of reaction vessel, and the rate of recovery of sulfide is far above general method.
Description of drawings
Fig. 1 is the graph of a relation between hydrogen sulfide generation and the pH value.
Fig. 2 and Fig. 3 are the synoptic diagram that reclaims sulfide and phi protein from depilation waste liquor provided by the invention.
1, reaction vessel inlet pipe
2, reaction vessel vapor pipe
3, add the sour container inlet pipe
4, add the sour container vapor pipe
5, advance/discharge nozzle
6, add the sour container lid
Specific implementation method
The present invention is further illustrated below in conjunction with embodiment.
The structure of retrieving arrangement as shown in Figure 2, the vapor pipe (4) that adds sour container links to each other with reaction vessel inlet pipe (1), reaction vessel vapor pipe (2) links to each other with absorption unit, the inlet pipe (3) that adds sour container links to each other with pressurized gas, wherein closed reaction vessel is that volume is 1000 liters a plastic tank, adding sour container is that volume is 50 liters a plastic tank, and the device of absorbing hydrogen sulphide gas is that two volumes respectively are 100 liters plastic tank.
Open closed reaction vessel enterprising/valve of discharge nozzle 5, with the 800kg depilation waste liquor by advance/discharge nozzle 5 joins in this container, close then into/valve of discharge nozzle 5.In the plastic tank of absorbing hydrogen sulphide gas device, respectively add 50kg concentration and be 8% NaOH solution.Analysis is the depilation waste liquor required hydrochloric acid content in the pH4 left and right sides that neutralizes, and will add in the sour container cover lid 6 afterwards after 3 times of the hydrochloric acid dilutions, and by shown in the accompanying drawing each container being connected with pipeline.
Reaction vessel vapor pipe 2 in the opening unit, add sour container inlet pipe 3 and add the valve of sour container vapor pipe 4, input pressure is the pressurized gas of 0.1MPa in adding sour container inlet pipe 3, utilize gaseous tension that acid solution is pressed in the depilation waste liquor in the closed reaction vessel, and the lasting pressurized gas that feeds stirs reaction system, the hydrogen sulfide that sulfide reaction in acid and the depilation waste liquor is produced is crossed reaction vessel vapor pipe 2 by air communication and is taken out of, and is absorbed back generation sodium sulphite by sodium hydroxide solution.
After 30 minutes, after checking that with plumbic acetate solution reaction vessel vapor pipe 2 no longer includes hydrogen sulfide and discharges, open into/valve of discharge nozzle 5, the valve of off-response vessel exhaust pipe 2, depilation waste liquor after utilizing the pressure of pressurized gas to handle by advance/discharge nozzle 5 extruded closed reaction vessel by air pressure, again by filtering or the protein that is precipitated out is reclaimed in centrifugation.
The structure of retrieving arrangement as shown in Figure 3, the vapor pipe (4) that adds sour container directly communicates with the reaction vessel body, the inlet pipe (3) that adds sour container all links to each other with pressurized gas with reaction vessel inlet pipe (1), reaction vessel vapor pipe (2) links to each other with absorption unit, wherein closed reaction vessel is to be 40 at subsurface, volume, 000 liter airtight cement pit, adding sour container is that volume is 2, the airtight cement pit that 000 liter, interior envelope are moulded, the device of absorbing hydrogen sulphide gas is that two volumes respectively are 2,000 liters airtight cement pit.
Open closed reaction vessel enterprising/valve of discharge nozzle 5, with 30, the 000kg depilation waste liquor by advance/discharge nozzle (5) joins in this container, close then into/valve of discharge nozzle 5.In the airtight cement pit of absorbing hydrogen sulphide gas device, respectively add 1,500kg water and 30kg lime.Analysis is the depilation waste liquor required hydrochloric acid content in the pH4 left and right sides that neutralizes, with good seal again after adding in the sour container after 5 times of the hydrochloric acid dilutions, and by shown in the accompanying drawing each cement container being connected with pipeline.
Reaction vessel vapor pipe 2 in the opening unit, add sour container inlet pipe 3 and the valve that adds sour container vapor pipe 4, input pressure is the pressurized gas of 0.5MPa in adding sour container inlet pipe 3, utilize gaseous tension that acid solution is pressed in the depilation waste liquor in the closed reaction vessel, closes compression gas then, continuing to feed pressurized gas by reaction vessel inlet pipe (1) simultaneously stirs reaction system, the hydrogen sulfide that sulfide reaction in acid and the depilation waste liquor is produced is crossed reaction vessel vapor pipe 2 by air communication and is taken out of, and is absorbed back generation sulfurated lime by lime solution.
After 30 minutes, after checking that with plumbic acetate solution reaction vessel vapor pipe 2 no longer includes hydrogen sulfide and discharges, open into/valve of discharge nozzle 5, the valve of off-response vessel exhaust pipe 2, depilation waste liquor after utilizing the pressure of pressurized gas to handle by advance/discharge nozzle 5 extruded closed reaction vessel by air pressure, again by filtering or the protein that is precipitated out is reclaimed in centrifugation.
Claims (10)
1. one kind is reclaimed sulfide and method of protein from the depilation waste liquor that tanning production produced, it is characterized in that depilation waste liquor is added in the closed reaction vessel, add acid, and the feeding pressurized gas stirs reaction system, make the sulfide reaction in acid and the depilation waste liquor produce hydrogen sulfide, and the air-flow that utilizes pressurized gas the to produce hydrogen sulfide that will react generation is taken reaction vessel out of and is reclaimed, the acid that is added simultaneously makes the pH value of depilation waste liquor adjust to 2～6, protein precipitation is come out and reclaims.
2. one kind is exclusively used in the device of implementing the described method of claim 1, it is characterized in that this device comprises a closed reaction vessel at least, one adds sour container and an absorption unit, described closed reaction vessel has a reaction vessel inlet pipe (1) at least, advancing/discharge nozzle (5) of the reaction vessel vapor pipe (2) of a band valve and a band valve, reaction vessel inlet pipe (1) and advancing/discharge nozzle (5) is positioned at the bottom of closed reaction vessel, reaction vessel vapor pipe (2) is positioned at the top of closed reaction vessel, reaction vessel inlet pipe (1) with add that sour container communicates or communicate with pressurized gas, reaction vessel vapor pipe (2) communicates with absorption unit, enters/discharge nozzle (5) and communicates with the external world.
3. device according to claim 2, it is characterized in that described add sour container have at least a band valve add sour container inlet pipe (3), a band valve add that sour container vapor pipe (4) and one can seal add sour container lid (6), add sour container inlet pipe (3) one ends and be positioned at the top that adds sour container, the other end communicates with pressurized gas, add sour container vapor pipe (4) one ends and be positioned at the bottom that adds sour container, the other end links to each other with described reaction vessel inlet pipe (1), or directly communicates with the reaction vessel body.
4. according to claim 2 or 3 described devices, it is characterized in that described absorption unit is container or the conventional absorption tower that basic solution is housed.
5. device according to claim 4, the concentration that it is characterized in that described basic solution is 0.1wt%～50wt%, used alkali is one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide, ammoniacal liquor, yellow soda ash and the sodium sulphite.
6. one kind is reclaimed sulfide and method of protein by device as described in claim 4 from the depilation waste liquor that tanning production produced, and it is characterized in that may further comprise the steps:
The vapor pipe (4) that 1. will add sour container links to each other with reaction vessel inlet pipe (1), and reaction vessel vapor pipe (2) links to each other with absorption unit;
2. open the valve of the advancing of closed reaction vessel/discharge nozzle (5), with depilation waste liquor by advance/discharge nozzle (5) is incorporated in this reaction vessel, closes into/discharge nozzle the valve of (5) then;
3. open and add sour container lid (6), acid solution after diluting 1～10 times is joined in the sour container, cover tight lid (6), utilize pressurized gas with acid solution by adding during sour container vapor pipe (4) is pressed in the closed reaction vessel that depilation waste liquor is housed, and the lasting pressurized gas that feeds stirs the reaction system in the closed reaction vessel, take the hydrogen sulfide that the reaction of the sulfide in acid and the depilation waste liquor is produced out of reaction vessel by reaction vessel vapor pipe (2) by the air-flow that pressurized gas produces, and, obtain the sulfide that can utilize again with the absorption of the basic solution in the absorption unit;
4. control the above-mentioned acid solution amount that adds, make the pH value of depilation waste liquor reach 2～6, the protein precipitation in the depilation waste liquor is come out;
5. after treating that hydrogen sulfide in the encloses container drains, open into/valve of discharge nozzle (5), the valve of off-response vessel exhaust pipe (2), depilation waste liquor after utilizing pressurized gas to produce air pressure will to handle by advance/discharge nozzle (5) extrudes encloses container, again by the protein that filters or the centrifugation recovery is precipitated out.
7. one kind is reclaimed sulfide and method of protein by device as described in claim 4 from the depilation waste liquor that tanning production produced, and it is characterized in that may further comprise the steps:
The vapor pipe (4) that 1. will add sour container directly communicates with the reaction vessel body, and reaction vessel inlet pipe (1) links to each other with pressurized gas, and reaction vessel vapor pipe (2) links to each other with absorption unit;
2. open the valve of the advancing of closed reaction vessel/discharge nozzle (5), with depilation waste liquor by advance/discharge nozzle (5) is incorporated in this reaction vessel, closes into/discharge nozzle the valve of (5) then;
3. open and add sour container lid (6), acid solution after diluting 1～10 times is joined in the sour container, cover tight lid (6), utilize pressurized gas with acid solution by add sour container vapor pipe (4) be pressed in the closed reaction vessel that depilation waste liquor is housed in closes compression gas then, continuing to feed pressurized gas by reaction vessel inlet pipe (1) simultaneously stirs the reaction system in the closed reaction vessel, take the hydrogen sulfide that the reaction of the sulfide in acid and the depilation waste liquor is produced out of reaction vessel by reaction vessel vapor pipe (2) by the air-flow that pressurized gas produces, and, obtain the sulfide that can utilize again with the absorption of the basic solution in the absorption unit;
4. control the above-mentioned acid solution amount that adds, make the pH value of depilation waste liquor reach 2～6, the protein precipitation in the depilation waste liquor is come out;
5. after treating that hydrogen sulfide in the encloses container drains, open into/valve of discharge nozzle (5), the valve of off-response vessel exhaust pipe (2), depilation waste liquor after utilizing pressurized gas to produce air pressure will to handle by advance/discharge nozzle (5) extrudes encloses container, again by the protein that filters or the centrifugation recovery is precipitated out.
8. according to claim 1,6 and 7 any one described method, it is characterized in that described acid is one or more in sulfuric acid, hydrochloric acid, nitric acid, formic acid, acetic acid and the phosphoric acid.
9. according to claim 6 or 7 described methods, the concentration that it is characterized in that described basic solution is 0.1wt%～50wt%, and used alkali is one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide, ammoniacal liquor, yellow soda ash and the sodium sulphite.
10. according to claim 1,6 and 7 any one described method, the pressure that it is characterized in that described pressurized gas is 0.001MPa～1MPa.
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| CN200710063497A CN101234753B (en) | 2007-02-02 | 2007-02-02 | Method and apparatus for recovering sulfide and protein from depilation waste liquor |
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| CN200710063497A CN101234753B (en) | 2007-02-02 | 2007-02-02 | Method and apparatus for recovering sulfide and protein from depilation waste liquor |
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| CN101234753B CN101234753B (en) | 2010-05-19 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108219862A (en) * | 2016-12-14 | 2018-06-29 | 广东韶钢松山股份有限公司 | The innoxious process for treating of vacuum condensation liquid |
| CN109052877A (en) * | 2018-08-02 | 2018-12-21 | 广州桑尼环保科技有限公司 | A kind of chromium mud resource reclaim and the method and system of waste residue harmless treatment |
| CN115504598A (en) * | 2022-09-21 | 2022-12-23 | 中国电建集团昆明勘测设计研究院有限公司 | Gelatin production workshop wastewater treatment and recycling process |
| CN115504598B (en) * | 2022-09-21 | 2024-05-14 | 中国电建集团昆明勘测设计研究院有限公司 | Wastewater treatment and recycling process for gelatin production workshop |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4085044A (en) * | 1977-05-27 | 1978-04-18 | The United States Of America As Represented By The Secretary Of Agriculture | Treatment of lime-sulfide tannery unhairing waste |
| CN85100819B (en) * | 1985-04-01 | 1988-08-10 | 武汉市皮革技术研究所 | New pollution-free tanning technology |
| US5328677A (en) * | 1992-06-17 | 1994-07-12 | Pvl Limited Partnership I | Recovery of sulfides from tannery waste liquor |
-
2007
- 2007-02-02 CN CN200710063497A patent/CN101234753B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108219862A (en) * | 2016-12-14 | 2018-06-29 | 广东韶钢松山股份有限公司 | The innoxious process for treating of vacuum condensation liquid |
| CN109052877A (en) * | 2018-08-02 | 2018-12-21 | 广州桑尼环保科技有限公司 | A kind of chromium mud resource reclaim and the method and system of waste residue harmless treatment |
| CN109052877B (en) * | 2018-08-02 | 2021-04-13 | 广州桑尼环保科技有限公司 | Method and system for recycling chromium sludge resources and harmlessly treating waste residues |
| CN115504598A (en) * | 2022-09-21 | 2022-12-23 | 中国电建集团昆明勘测设计研究院有限公司 | Gelatin production workshop wastewater treatment and recycling process |
| CN115504598B (en) * | 2022-09-21 | 2024-05-14 | 中国电建集团昆明勘测设计研究院有限公司 | Wastewater treatment and recycling process for gelatin production workshop |
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| CN101234753B (en) | 2010-05-19 |
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