CN104448036B - A kind of regeneration method of waste hydrochloric acid in chitin production process - Google Patents
A kind of regeneration method of waste hydrochloric acid in chitin production process Download PDFInfo
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Abstract
The invention belongs to trade waste regenerative use technology field, specifically disclose a kind of regeneration method of waste hydrochloric acid in chitin production process.After the present invention carries out Regeneration Treatment by the waste hydrochloric acid solution after processing first time decalcification operation, it is directly used in second time decalcification to process, waste hydrochloric acid solution after decalcification for the second time processes processes for third time decalcification after Regeneration Treatment, recycle successively, the reaction vigor that can make each reacted hydrochloric acid solution can return to the level close to fresh hydrochloric acid, really realize the recycling of hydrochloric acid, and the more important thing is, other decalcification operations in addition to first step decalcification processes all need not the most additionally add hydrochloric acid, also can guarantee that decalcification efficiency and effect.So can reduce the last generation amount producing waste water, it is achieved the cleaning of chitin produces.
Description
Technical field
The invention belongs to trade waste regenerative use technology field, be specifically related to the regeneration side of a kind of waste hydrochloric acid
Method, is more particularly to a kind of regeneration method of waste hydrochloric acid in chitin production process.
Background technology
Chitin is also called chitin, chitin, chemical entitled β-(1-4)-2-acetylaminohydroxyphenylarsonic acid 2-deoxy-D-glucose,
In weaving, chemical industry, food, medicine and other fields, there is important application prospect.Chitin be primarily present in rudimentary plant mushroom,
The shell of crustacean, the cell wall etc. of fungus such as shrimp, Eriocheir sinensis, insecticide.The primary raw material of industrialized production is shrimp, Carapax Eriocheir sinensis at present.
The production process of chitin mainly has two operations, first operation to be decalcification operations, the ash in shrimp, Carapax Eriocheir sinensis
Dividing mainly calcium carbonate, the subtractive process of calcium carbonate is to join in certain density hydrochloric acid by shrimp, Carapax Eriocheir sinensis, carbon in shrimp, Carapax Eriocheir sinensis
Acid calcium and hydrochloric acid reaction are changed into the calcium chloride of solubility, thus remove the calcium carbonate in shrimp, Carapax Eriocheir sinensis；Another committed step is
The removing of the protein in prawn, Carapax Eriocheir sinensis, traditional method for removing protein is that shrimp, Carapax Eriocheir sinensis are joined dilute hydrogen that concentration is 4%-10%
In sodium hydroxide solution, soak 3-5 hour at 60 DEG C, proteolytic therein is removed.
During decalcification, for ensureing that the ash of chitin is reduced to regulation requirement, need to add the hydrochloric acid of excess, thus
Thoroughly remove the calcium in shrimp, Carapax Eriocheir sinensis, therefore decalcification waste liquid has substantial amounts of hydrochloric acid to remain.
Conventional treatment method to hydrochloride waste is by waste hydrochloric acid solution reuse at present, and concrete way is that waste hydrochloric acid is molten
Liquid and the raw material reaction not having decalcification, the calcium carbonate reaction in remaining hydrochloric acid and shrimp, Carapax Eriocheir sinensis in waste hydrochloric acid solution, carry out pre-de-
Calcium treatment.Along with the reduction of concentration of hydrochloric acid, response speed is gradually reduced, and last remaining hydrochloric acid sodium hydroxide neutralizes.Centering
Waste liquid after with processes further, rear discharge up to standard.This traditional spent acid processing method, hydrochloric acid wastage is big, neutralizes spent acid
Needing to expend substantial amounts of sodium hydroxide, processing cost is high, and waste water generation amount is big, and in waste water, salt ion content is high, enters waste water
One step processes and adversely affects.
Application publication number is that the patent document of CN101974103A discloses a kind of clean preparation process of chitin, special at this
Profit file describes employing dynamic circulation in pickling workshop section, acid solution is reused, recycle and reach more than 5 times,
Making the calcareous content in waste water tend in saturated backward waste water and add sulphuric acid again, filter, obtain calcium sulfate, acid waste water reclaims and is used for
Preparation hydrochloric acid solution is used.In this patent document, the hydrochloric acid being the basis of the recycling of acid solution in acid solution is excessive,
Utilize remaining hydrochloric acid to react with prawn head Crusta Penaeus seu Panulirus again, remove calcium carbonate therein.It is molten that its essence does not breaks away from traditional waste hydrochloric acid yet
The pre-decalcification of liquid processing method waste hydrochloric acid solution processes, only in the production technology of this patent document chitin, and salt
The remaining amount of acid is bigger, and (surplus is mainly contributed by big solid-liquid ratio 1:8-1:12, and in industrial processes, solid-liquid ratio is generally
About 1:2.6), so more than 5 times could be circulated.Cycle-index is the most, needs the amount remaining hydrochloric acid in waste hydrochloric acid solution the most,
Along with the reduction of concentration of hydrochloric acid in acid solution, reaction efficiency and decalcification effect decline, therefore decalcification process needs 10-15 hour.
When hydrochloric acid dynamic circulation ends, adding sulphuric acid, filter, obtain calcium sulfate in waste water, acid waste water is used for returning complex acid liquid use,
Patent document only achieves the reuse of acid waste water.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, it is provided that the side that in a kind of chitin production process, waste hydrochloric acid regeneration utilizes
Method.After the present invention carries out Regeneration Treatment to the waste hydrochloric acid solution after the process of first time decalcification operation, it is directly used in second time decalcification
Processing, the waste hydrochloric acid solution after decalcification for the second time processes processes for third time decalcification after Regeneration Treatment, and circulation makes successively
With, the reaction vigor of each reacted hydrochloric acid solution can be made can to return to the level close to fresh hydrochloric acid, hydrochloric acid can weigh
Multiple utilization, and the more important thing is, other decalcification operations in addition to first step decalcification processes all need not the most additionally add salt
Acid, also can guarantee that decalcification efficiency and effect.
The purpose of the present invention is achieved by the following technical programs:
A kind of regeneration method of waste hydrochloric acid in chitin production process, described method comprises the steps:
Regeneration Treatment for the first time: collected the waste hydrochloric acid solution after decalcification operation processes for the first time, waste hydrochloric acid solution warp
After filtering and impurity removing, in waste hydrochloric acid solution, add sulfuric acid solution, calcium ion and the mol ratio adding sulfate radical in waste hydrochloric acid solution
For 1:0.4-2.3；Regeneration of hydrochloric acid is realized through precipitation, growing the grain, filtration；Hydrochloric acid after regeneration need not it is possible to additionally incorporate hydrochloric acid can be direct
Process for second time decalcification；
N-th Regeneration Treatment: collected the waste hydrochloric acid solution after n-th decalcification operation processes, waste hydrochloric acid solution passes through
Filter miscellaneous after, in waste hydrochloric acid solution add sulfuric acid solution, in waste hydrochloric acid solution calcium ion with addition sulfate radical mol ratio be
1:0.4-2.3；Regeneration of hydrochloric acid is realized through precipitation, growing the grain, filtration；Hydrochloric acid after regeneration need not it is possible to additionally incorporate hydrochloric acid and can directly use
Process in the N+1 time decalcification；N is the natural number more than or equal to 2, repeats Regeneration Treatment, until regenerant salt acid solution can not be located again
Till reason makes chitin ash≤3.0%.
In chitin production process, collect waste hydrochloric acid after each decalcification operation processes, add moderate amount of sulfuric acid, control waste hydrochloric acid
In solution calcium ion with add the mol ratio of sulfate radical, carry out the regeneration of hydrochloric acid solution, and decalcification operation once after being used for, often
The reaction vigor of the hydrochloric acid solution after secondary response can return to the level close to fresh hydrochloric acid, the repeatable utilization of hydrochloric acid, is not required to
Hydrochloric acid to be added, it is ensured that decalcification efficiency and effect, reduces the generation amount of waste water simultaneously, it is achieved the cleaning of chitin produces.
Preferably, the mass concentration of described sulfuric acid solution is 40-98%.
Preferably, the step of described precipitation is addition sulfuric acid solution, mixing speed in the discarded hydrochloric acid after filtering and impurity removing
20-60 rpm, stirring while adding, sulphuric acid added in 30 minutes, after sulphuric acid adds, continued stirring 10-30 minute, made anti-
Should be complete.
Preferably, described growing the grain step is, after precipitation terminates, waste hydrochloric acid and sulfuric acid mixture is stood 1-3 little
Time, carry out growing the grain process.Operating according to the method, calcium sulfate precipitation forms bigger crystallization, beneficially filter operation.
Preferably, described N is 3,4,5,6,7,8.Regenerative process as N=5 is: the 1st Regeneration Treatment, collection completes
Waste hydrochloric acid solution after 1st time decalcification operation processes, after filtering and impurity removing, adds sulfuric acid solution, abraum salt in waste hydrochloric acid solution
In acid solution, calcium ion is 1:0.4-2.3 with the mol ratio of addition sulfate radical；Regeneration of hydrochloric acid is realized through precipitation, growing the grain, filtration；Again
Hydrochloric acid after life need not it is possible to additionally incorporate hydrochloric acid and can be directly used for the 2nd decalcification process；
2nd Regeneration Treatment: having collected the waste hydrochloric acid solution after the 2nd decalcification operation processes, waste hydrochloric acid solution passes through
Filter miscellaneous after, in waste hydrochloric acid solution add sulfuric acid solution, in waste hydrochloric acid solution calcium ion with addition sulfate radical mol ratio be
1:0.4-2.3；Regeneration of hydrochloric acid is realized through precipitation, growing the grain, filtration；Hydrochloric acid after regeneration need not it is possible to additionally incorporate hydrochloric acid and can directly use
Process in the 3rd decalcification；
3rd Regeneration Treatment: having collected the waste hydrochloric acid solution after the 3rd decalcification operation processes, waste hydrochloric acid solution passes through
Filter miscellaneous after, in waste hydrochloric acid solution add sulfuric acid solution, in waste hydrochloric acid solution calcium ion with addition sulfate radical mol ratio be
1:0.4-2.3；Regeneration of hydrochloric acid is realized through precipitation, growing the grain, filtration；Hydrochloric acid after regeneration need not it is possible to additionally incorporate hydrochloric acid and can directly use
Process in the 4th decalcification；
The 4th Regeneration Treatment: collected the waste hydrochloric acid solution after the 4th decalcification operation processes, waste hydrochloric acid solution passes through
Filter miscellaneous after, in waste hydrochloric acid solution add sulfuric acid solution, in waste hydrochloric acid solution calcium ion with addition sulfate radical mol ratio be
1:0.4-2.3；Regeneration of hydrochloric acid is realized through precipitation, growing the grain, filtration；Hydrochloric acid after regeneration need not it is possible to additionally incorporate hydrochloric acid and can directly use
Process in the 5th decalcification；
The 5th Regeneration Treatment: collected the waste hydrochloric acid solution after the 5th decalcification operation processes, waste hydrochloric acid solution passes through
Filter miscellaneous after, in waste hydrochloric acid solution add sulfuric acid solution, in waste hydrochloric acid solution calcium ion with addition sulfate radical mol ratio be
1:0.4-2.3；Regeneration of hydrochloric acid is realized through precipitation, growing the grain, filtration；Hydrochloric acid after regeneration need not it is possible to additionally incorporate hydrochloric acid and can directly use
Process in the 6th decalcification.
Preferably, the reaction temperature of described method is room temperature.
Preferably, employing sucking filtration, centrifugal filtration or filter pressing are filtered described in S1 and S4.
Preferably, stir process described in S2 is carried out in the enamel reaction still of band agitating device, and described reactor is internal to be coated with
There is ceramic layer, it is to avoid by acid corrosion.
Compared with prior art, there is advantages that
(1) the waste hydrochloric acid solution after each decalcification operation is processed by the method for the invention regenerates, and regeneration hydrochloric acid can
Recycling, it is not necessary to add hydrochloric acid, it is ensured that decalcification efficiency and effect, reduce the generation amount of waste water, it is achieved chitin simultaneously
Cleaning produces.
(2) present invention has broken away from the processing method of traditional waste hydrochloric acid, the bar of normal hydrochloric consumption needed for industrialized production
Under part (5.1wt%, dry shrimp head Crusta Penaeus seu Panulirus is 1:13 with the solid-liquid ratio of hydrochloric acid solution, and the water content of wet prawn head Crusta Penaeus seu Panulirus is about 80%,
If the solid-liquid ratio being scaled wet prawn head Crusta Penaeus seu Panulirus is 1:2.6), the recycling utilization of hydrochloric acid can be realized.
(3) present invention is to calcium ion in solution and the mol ratio adding sulphuric acid, the concentration of sulphuric acid, reacts mixing speed, instead
Between Ying Shi, the standing rearing crystal time etc. of calcium sulfate precipitation has strict requirements, it is to avoid misoperation makes whole waste hydrochloric acid molten
Liquid presents pasty state, causes regenerating the unsuccessfully phenomenon that cannot reuse, it is achieved that the recycling utilization of hydrochloric acid, with former
, there is essential distinction in the reuse of inventive method acid waste water.
(4) regenerant salt acid solution of the present invention decalcification operation in chitin production process can be circulated use, time
Short, efficiency is high.
(5) present invention can reduce chitin production cost, significantly improves the productivity effect of chitin enterprise；Reduce carapace
Waste water generation amount in element production process, reduces environmental pollution, has preferable economic benefit and social benefit.
Accompanying drawing explanation
Fig. 1 is the regeneration schematic flow sheet of waste hydrochloric acid of the present invention.
Detailed description of the invention
Below in conjunction with Figure of description and specific embodiment, the present invention is described in further details, but embodiment is the most right
The present invention limits in any form.Unless stated otherwise, the present invention uses reagent, method and apparatus are that the art is normal
Rule reagent, method and apparatus.
Embodiment 1
Regeneration for the first time
Being joined by dry Crusta Penaeus seu Panulirus in the hydrochloric acid solution that concentration is 5.1wt%, the amount of addition is 1:13(mass volume ratio), room
The lower stirring reaction of temperature 4 hours, carries out the decalcification reaction of Crusta Penaeus seu Panulirus.The Crusta Penaeus seu Panulirus after decalcification is isolated in reaction after terminating, obtain decalcification and give up
Hydrochloric acid solution.It is filtered to remove the chitin in waste hydrochloric acid solution, fiber, stone solid sundries, obtains decalcification waste hydrochloric acid solution, survey
Obtaining calcium ion concentration in this hydrochloric acid solution is 0.13 mole every liter, takes waste hydrochloric acid solution 1000 liters, and adding volume is 2 cubes
In enamel reaction still, start motor and be stirred, be 1:1.2 by calcium ion and sulfate radical mol ratio, be slowly added to 80% concentration
Sulfuric acid solution 19.2 kilograms, stirring while adding, mixing speed is 30 rpms, and sulphuric acid added in 30 minutes, and sulphuric acid adds
After, continue stirring reaction 30 minutes.After reaction terminates, stopping stirring, mixture stands 2 hours, and calcium sulfate precipitation is passed through plate
Frame filter is filtered to remove, and obtains the first time regenerant salt acid solution of clarification.Regenerant salt acid solution is by the decalcification work of fresh hydrochloric acid
Skill condition carries out the decalcification of Crusta Penaeus seu Panulirus and processes, and the Crusta Penaeus seu Panulirus after decalcification is carried out deproteinization process, obtains chitin, obtain after drying
Chitin ash is 0.34%.
Regeneration for the second time
Take the waste hydrochloric acid solution after for the first time regenerant salt acid solution decalcification, be filtered to remove the chitin in waste hydrochloric acid solution,
Fiber, stone solid sundries, recording calcium ion concentration in this hydrochloric acid solution is 0.17 mole every liter, takes waste hydrochloric acid solution 800 liters,
Add in the enamel reaction still that volume is 2 cubes, start motor and be stirred, be 1 by calcium ion and sulfate radical mol ratio:
1.2, it is slowly added to the sulfuric acid solution 16.4 kilograms of 98% concentration, stirring while adding, mixing speed is 30 rpms, and sulphuric acid exists
Add in 30 minutes, after sulphuric acid adds, continue stirring reaction 30 minutes.After reaction terminates, stopping stirring, mixture stands 2.5
Hour, calcium sulfate precipitation is filtered to remove by flame filter press, obtains the second time regenerant salt acid solution of clarification.Regeneration hydrochloric acid
The decalcification that solution carries out Crusta Penaeus seu Panulirus by the decalcification process conditions of fresh hydrochloric acid processes, and the Crusta Penaeus seu Panulirus after decalcification is carried out deproteinization process,
Obtaining chitin after drying, the chitin ash obtained is 0.41%.
Regeneration for the third time
Take second time regenerant salt acid solution decalcification after waste hydrochloric acid solution, be filtered to remove the chitin in waste hydrochloric acid solution,
Fiber, stone solid sundries, obtain decalcification waste hydrochloric acid solution, record calcium ion concentration in this hydrochloric acid solution be 0.16 mole every
Rise, take waste hydrochloric acid solution 700 liters, add in the enamel reaction still that volume is 2 cubes, start motor and be stirred, by calcium from
Son and sulfate radical mol ratio are 1:0.4, are slowly added to the sulfuric acid solution 11.0 kilograms of 40% concentration, stirring while adding, mixing speed
Being 20 rpms, sulphuric acid added in 30 minutes, after sulphuric acid adds, continued stirring reaction 15 minutes.After reaction terminates, stop
Stirring, mixture is stood 1.5 hours, is filtered to remove by flame filter press by calcium sulfate precipitation, obtains the third time of clarification again
Sal acid solution.The decalcification that regenerant salt acid solution carries out Crusta Penaeus seu Panulirus by the decalcification process conditions of fresh hydrochloric acid processes, after decalcification
Crusta Penaeus seu Panulirus carries out deproteinization process, obtains chitin after drying, and the chitin ash obtained is 0.45%.
Embodiment 2
Regeneration for the first time
Dry shrimp head after drying joins in the hydrochloric acid solution that concentration is 5.1wt%, and the amount of addition is 1:13(mass body
Long-pending ratio), stirring reaction 4 hours under room temperature, carry out the decalcification reaction of Crusta Penaeus seu Panulirus.The prawn head after decalcification is isolated in reaction after terminating,
To decalcification waste hydrochloric acid solution.It is filtered to remove the chitin in waste hydrochloric acid solution, fiber, stone solid sundries, obtains decalcification abraum salt
Acid solution, recording calcium ion concentration in this hydrochloric acid solution is 0.12 mole every liter, takes waste hydrochloric acid solution 1000 liters, adds volume and is
In the enamel reaction still of 2 cubes, start motor and be stirred, be 1:1.2 by calcium ion and sulfate radical mol ratio, be slowly added to
The sulfuric acid solution of 90% concentration 15.7 kilograms, stirring while adding, mixing speed is 50 rpms, and sulphuric acid added in 30 minutes,
After sulphuric acid adds, continue stirring reaction 20 minutes.After reaction terminates, stopping stirring, mixture stands 3 hours, is sunk by calcium sulfate
Form sediment and be filtered to remove by flame filter press, obtain the first time regenerant salt acid solution of clarification.Regenerant salt acid solution presses fresh hydrochloric acid
Decalcification process conditions carry out prawn head decalcification process, the prawn head after decalcification is carried out deproteinization process, after drying, obtains carapace
Element, the chitin ash obtained is 0.32%.
Regeneration for the second time
Take the waste hydrochloric acid solution after for the first time regeneration hydrochloric acid decalcification, be filtered to remove the chitin in waste hydrochloric acid solution, fiber,
Stone solid sundries, obtains decalcification waste hydrochloric acid solution, and recording calcium ion concentration in this hydrochloric acid solution is 0.16 mole every liter, takes useless
Hydrochloric acid solution 800 liters, adds in the enamel reaction still that volume is 2 cubes, starts motor and be stirred, by calcium ion and sulphuric acid
Root mol ratio is 1:1.0, is slowly added to the sulfuric acid solution 7.0 kilograms of 90% concentration, stirring while adding, mixing speed be 50 turns every
Minute, sulphuric acid added in 30 minutes, after sulphuric acid adds, continued stirring reaction 15 minutes.After reaction terminates, stop stirring, mixed
Compound stands 1 hour, is filtered to remove by flame filter press by calcium sulfate precipitation, and the second time regeneration hydrochloric acid obtaining clarification is molten
Liquid.The decalcification that regenerant salt acid solution carries out prawn head by the decalcification process conditions of fresh hydrochloric acid processes, and carries out the prawn head after decalcification
Deproteinization processes, and obtains chitin after drying, and the chitin ash obtained is 0.38%.
Regeneration for the third time
Take second time regeneration hydrochloric acid decalcification after waste hydrochloric acid solution, be filtered to remove the chitin in waste hydrochloric acid solution, fiber,
Stone solid sundries, obtains decalcification waste hydrochloric acid solution, and recording calcium ion concentration in this hydrochloric acid solution is 0.15 mole every liter, takes useless
Hydrochloric acid solution 700 liters, adds in the enamel reaction still that volume is 2 cubes, starts motor and be stirred, by calcium ion and sulphuric acid
Root mol ratio is 1:0.5, is slowly added to the sulfuric acid solution 10.3 kilograms of 50% concentration, stirring while adding, mixing speed be 25 turns every
Minute, sulphuric acid added in 30 minutes, after sulphuric acid adds, continued stirring reaction 18 minutes.After reaction terminates, stop stirring, mixed
Compound stands 2.5 hours, is filtered to remove by flame filter press by calcium sulfate precipitation, and the third time regeneration hydrochloric acid obtaining clarification is molten
Liquid.The decalcification that regenerant salt acid solution carries out prawn head by the decalcification process conditions of fresh hydrochloric acid processes, and carries out the prawn head after decalcification
Deproteinization processes, and obtains chitin after drying, and the chitin ash obtained is 0.46%.
4th regeneration
Take third time regeneration hydrochloric acid decalcification after waste hydrochloric acid solution, be filtered to remove the chitin in waste hydrochloric acid solution, fiber,
Stone solid sundries, obtains decalcification waste hydrochloric acid solution, and recording calcium ion concentration in this hydrochloric acid solution is 0.12 mole every liter, takes useless
Hydrochloric acid solution 500 liters, adds in the enamel reaction still that volume is 2 cubes, starts motor and be stirred, by calcium ion and sulphuric acid
Root mol ratio is 1:2.3, is slowly added to the sulfuric acid solution 22.5 kilograms of 60% concentration, stirring while adding, mixing speed be 40 turns every
Minute, sulphuric acid added in 30 minutes, after sulphuric acid adds, continued stirring reaction 12 minutes.After reaction terminates, stop stirring, mixed
Compound stands 2.5 hours, is filtered to remove by flame filter press by calcium sulfate precipitation, and the 4th the regeneration hydrochloric acid obtaining clarification is molten
Liquid.The decalcification that regenerant salt acid solution carries out prawn head by the decalcification process conditions of fresh hydrochloric acid processes, and carries out the prawn head after decalcification
Deproteinization processes, and obtains chitin after drying, and the chitin ash obtained is 0.51%.
5th regeneration
Take the 4th time regeneration hydrochloric acid decalcification after waste hydrochloric acid solution, be filtered to remove the chitin in waste hydrochloric acid solution, fiber,
Stone solid sundries, obtains decalcification waste hydrochloric acid solution, and recording calcium ion concentration in this hydrochloric acid solution is 0.13 mole every liter, takes useless
Hydrochloric acid solution 400 liters, adds in the enamel reaction still that volume is 1 cube, starts motor and be stirred, by calcium ion and sulphuric acid
Root mol ratio is 1:0.9, is slowly added to the sulfuric acid solution 4.7 kilograms of 98% concentration, stirring while adding, mixing speed be 60 turns every
Minute, sulphuric acid added in 30 minutes, after sulphuric acid adds, continued stirring reaction 30 minutes.After reaction terminates, stop stirring, mixed
Compound stands 2 hours, is filtered to remove by flame filter press by calcium sulfate precipitation, and the 5th the regeneration hydrochloric acid obtaining clarification is molten
Liquid.The decalcification that regenerant salt acid solution carries out prawn head by the decalcification process conditions of fresh hydrochloric acid processes, and carries out the prawn head after decalcification
Deproteinization processes, and obtains chitin after drying, and the chitin ash obtained is 0.81%.
Embodiment 3
Regeneration for the first time
Dry Crusta Penaeus seu Panulirus after drying joins in the hydrochloric acid solution that concentration is 5.1wt%, and the amount of addition is 1:13(mass body
Long-pending ratio), stirring reaction 4 hours under room temperature, carry out the decalcification reaction of Crusta Penaeus seu Panulirus.The Crusta Penaeus seu Panulirus after decalcification is isolated in reaction after terminating,
To decalcification waste hydrochloric acid solution.It is filtered to remove the chitin in waste hydrochloric acid solution, fiber, stone solid sundries, obtains decalcification abraum salt
Acid solution, recording calcium ion concentration in this hydrochloric acid solution is 0.13 mole every liter, takes waste hydrochloric acid solution 2000 liters, adds volume and is
In the enamel reaction still of 3 cubes, start motor and be stirred, be 1:1.1 by calcium ion and sulfate radical mol ratio, be slowly added to
The sulfuric acid solution of 92% concentration 30.5 kilograms, stirring while adding, mixing speed is 50 rpms, and sulphuric acid added in 30 minutes,
After sulphuric acid adds, continue stirring reaction 20 minutes.After reaction terminates, stopping stirring, mixture stands 3 hours, is sunk by calcium sulfate
Form sediment and be filtered to remove by flame filter press, obtain the first time regenerant salt acid solution of clarification.Regenerant salt acid solution presses fresh hydrochloric acid
Decalcification process conditions carry out Crusta Penaeus seu Panulirus decalcification process, the Crusta Penaeus seu Panulirus after decalcification is carried out deproteinization process, after drying, obtains carapace
Element, the chitin ash obtained is 0.35%.
Regeneration for the second time
Take the waste hydrochloric acid solution after for the first time regeneration hydrochloric acid decalcification, be filtered to remove the chitin in waste hydrochloric acid solution, fiber,
Stone solid sundries, obtains decalcification waste hydrochloric acid solution, and recording calcium ion concentration in this hydrochloric acid solution is 0.16 mole every liter, takes useless
Hydrochloric acid solution 1700 liters, adds in the enamel reaction still that volume is 3 cubes, starts motor and be stirred, by calcium ion and sulfur
Acid group mol ratio is 1:1.0, is slowly added to the sulfuric acid solution 29.5 kilograms of 90% concentration, and stirring while adding, mixing speed is 50 turns
Per minute, sulphuric acid added in 30 minutes, after sulphuric acid adds, continued stirring reaction 25 minutes.After reaction terminates, stop stirring,
Mixture stands 2 hours, is filtered to remove by flame filter press by calcium sulfate precipitation, and the second time regeneration hydrochloric acid obtaining clarification is molten
Liquid.The decalcification that regenerant salt acid solution carries out Crusta Penaeus seu Panulirus by the decalcification process conditions of fresh hydrochloric acid processes, and carries out the Crusta Penaeus seu Panulirus after decalcification
Deproteinization processes, and obtains chitin after drying, and the chitin ash obtained is 0.39%.
Regeneration for the third time
Take second time regeneration hydrochloric acid decalcification after waste hydrochloric acid solution, be filtered to remove the chitin in waste hydrochloric acid solution, fiber,
Stone solid sundries, obtains decalcification waste hydrochloric acid solution, and recording calcium ion concentration in this hydrochloric acid solution is 0.15 mole every liter, takes useless
Hydrochloric acid solution 1500 liters, adds in the enamel reaction still that volume is 3 cubes, starts motor and be stirred, by calcium ion and sulfur
Acid group mol ratio is 1:0.6, is slowly added to the sulfuric acid solution 26.5 kilograms of 50% concentration, and stirring while adding, mixing speed is 20 turns
Per minute, sulphuric acid added in 30 minutes, after sulphuric acid adds, continued stirring reaction 18 minutes.After reaction terminates, stop stirring,
Mixture stands 2 hours, is filtered to remove by flame filter press by calcium sulfate precipitation, and the third time regeneration hydrochloric acid obtaining clarification is molten
Liquid.The decalcification that regenerant salt acid solution carries out Crusta Penaeus seu Panulirus by the decalcification process conditions of fresh hydrochloric acid processes, and carries out the Crusta Penaeus seu Panulirus after decalcification
Deproteinization processes, and obtains chitin after drying, and the chitin ash obtained is 0.45%.
4th regeneration
Take second time regeneration hydrochloric acid decalcification after waste hydrochloric acid solution, be filtered to remove the chitin in waste hydrochloric acid solution, fiber,
Stone solid sundries, obtains decalcification waste hydrochloric acid solution, and recording calcium ion concentration in this hydrochloric acid solution is 0.16 mole every liter, takes useless
Hydrochloric acid solution 1200 liters, adds in the enamel reaction still that volume is 3 cubes, starts motor and be stirred, by calcium ion and sulfur
Acid group mol ratio is 1:2.1, is slowly added to the sulfuric acid solution 65.9 kilograms of 60% concentration, and stirring while adding, mixing speed is 28 turns
Per minute, sulphuric acid added in 30 minutes, after sulphuric acid adds, continued stirring reaction 10 minutes.After reaction terminates, stop stirring,
Mixture stands 2.5 hours, is filtered to remove by flame filter press by calcium sulfate precipitation, obtains the 4th regeneration hydrochloric acid of clarification
Solution.The decalcification that regenerant salt acid solution carries out Crusta Penaeus seu Panulirus by the decalcification process conditions of fresh hydrochloric acid processes, and enters the Crusta Penaeus seu Panulirus after decalcification
Row deproteinization processes, and obtains chitin after drying, and the chitin ash obtained is 0.55%.
5th regeneration
Take the 4th time regeneration hydrochloric acid decalcification after waste hydrochloric acid solution, be filtered to remove the chitin in waste hydrochloric acid solution, fiber,
Stone solid sundries, obtains decalcification waste hydrochloric acid solution, and recording calcium ion concentration in this hydrochloric acid solution is 0.14 mole every liter, takes useless
Hydrochloric acid solution 1000 liters, adds in the enamel reaction still that volume is 3 cubes, starts motor and be stirred, by calcium ion and sulfur
Acid group mol ratio is 1:0.8, is slowly added to the sulfuric acid solution 13.7 kilograms of 80% concentration, and stirring while adding, mixing speed is 44 turns
Per minute, sulphuric acid added in 30 minutes, after sulphuric acid adds, continued stirring reaction 27 minutes.After reaction terminates, stop stirring,
Mixture stands 2 hours, is filtered to remove by flame filter press by calcium sulfate precipitation, and the 5th the regeneration hydrochloric acid obtaining clarification is molten
Liquid.The decalcification that regenerant salt acid solution carries out Crusta Penaeus seu Panulirus by the decalcification process conditions of fresh hydrochloric acid processes, and carries out the Crusta Penaeus seu Panulirus after decalcification
Deproteinization processes, and obtains chitin after drying, and the chitin ash obtained is 0.79%.
6th regeneration
Take the 5th time regeneration hydrochloric acid decalcification after waste hydrochloric acid solution, be filtered to remove the chitin in waste hydrochloric acid solution, fiber,
Stone solid sundries, obtains decalcification waste hydrochloric acid solution, and recording calcium ion concentration in this hydrochloric acid solution is 0.15 mole every liter, takes useless
Hydrochloric acid solution 800 liters, adds in the enamel reaction still that volume is 3 cubes, starts motor and be stirred, by calcium ion and sulphuric acid
Root mol ratio is 1:0.7, is slowly added to the sulfuric acid solution 16.5 kilograms of 50% concentration, stirring while adding, mixing speed be 20 turns every
Minute, sulphuric acid added in 30 minutes, after sulphuric acid adds, continued stirring reaction 20 minutes.After reaction terminates, stop stirring, mixed
Compound stands 2 hours, is filtered to remove by flame filter press by calcium sulfate precipitation, and the third time regeneration hydrochloric acid obtaining clarification is molten
Liquid.The decalcification that regenerant salt acid solution carries out Crusta Penaeus seu Panulirus by the decalcification process conditions of fresh hydrochloric acid processes, and carries out the Crusta Penaeus seu Panulirus after decalcification
Deproteinization processes, and obtains chitin after drying, and the chitin ash obtained is 1.15%.
7th regeneration
Take the 6th time regeneration hydrochloric acid decalcification after waste hydrochloric acid solution, be filtered to remove the chitin in waste hydrochloric acid solution, fiber,
Stone solid sundries, obtains decalcification waste hydrochloric acid solution, and recording calcium ion concentration in this hydrochloric acid solution is 0.16 mole every liter, takes useless
Hydrochloric acid solution 700 liters, adds in the enamel reaction still that volume is 3 cubes, starts motor and be stirred, by calcium ion and sulphuric acid
Root mol ratio is 1:2.1, is slowly added to the sulfuric acid solution 28.8 kilograms of 80% concentration, stirring while adding, mixing speed be 25 turns every
Minute, sulphuric acid added in 30 minutes, after sulphuric acid adds, continued stirring reaction 15 minutes.After reaction terminates, stop stirring, mixed
Compound stands 2 hours, is filtered to remove by flame filter press by calcium sulfate precipitation, and the 4th the regeneration hydrochloric acid obtaining clarification is molten
Liquid.The decalcification that regenerant salt acid solution carries out Crusta Penaeus seu Panulirus by the decalcification process conditions of fresh hydrochloric acid processes, and carries out the Crusta Penaeus seu Panulirus after decalcification
Deproteinization processes, and obtains chitin after drying, and the chitin ash obtained is 1.52%.
8th regeneration
Take the 7th time regeneration hydrochloric acid decalcification after waste hydrochloric acid solution, be filtered to remove the chitin in waste hydrochloric acid solution, fiber,
Stone solid sundries, obtains decalcification waste hydrochloric acid solution, and recording calcium ion concentration in this hydrochloric acid solution is 0.14 mole every liter, takes useless
Hydrochloric acid solution 500 liters, adds in the enamel reaction still that volume is 3 cubes, starts motor and be stirred, by calcium ion and sulphuric acid
Root mol ratio is 1:0.8, is slowly added to the sulfuric acid solution 5.6 kilograms of 98% concentration, stirring while adding, mixing speed be 35 turns every
Minute, sulphuric acid added in 30 minutes, after sulphuric acid adds, continued stirring reaction 20 minutes.After reaction terminates, stop stirring, mixed
Compound stands 1.5 hours, is filtered to remove by flame filter press by calcium sulfate precipitation, and the 8th the regeneration hydrochloric acid obtaining clarification is molten
Liquid.The decalcification that regenerant salt acid solution carries out Crusta Penaeus seu Panulirus by the decalcification process conditions of fresh hydrochloric acid processes, and carries out the Crusta Penaeus seu Panulirus after decalcification
Deproteinization processes, and obtains chitin after drying, and the chitin ash obtained is 2.05%.
Table 1 hydrochloric acid recycling table
Note: 1, solid-liquid ratio is the mass volume ratio of dry shrimp head and hydrochloric acid solution；The dry matter content of wet prawn head Crusta Penaeus seu Panulirus is 20%
Left and right.
2, "-" represents and is added without new hydrochloric acid.
According to country marine industry standard SC/T3403-2004 chitin quality index, food stage chitin ash≤
1.0%, technical grade chitin ash≤3.0%, the hydrochloric acid hence with present invention regeneration carries out the decalcification process of chitin completely
Disclosure satisfy that the prescription of chitin.
Claims (4)
1. the regeneration method of waste hydrochloric acid in a chitin production process, it is characterised in that comprise the steps:
Regeneration Treatment for the first time: collected the waste hydrochloric acid solution after decalcification operation processes for the first time, waste hydrochloric acid solution is through filtering
After remove impurity, adding sulfuric acid solution in waste hydrochloric acid solution, in waste hydrochloric acid solution, calcium ion is 1 with the mol ratio of addition sulfate radical:
0.4-2.3；Regeneration of hydrochloric acid is realized through precipitation, growing the grain, filtration；Hydrochloric acid after regeneration need not it is possible to additionally incorporate hydrochloric acid and can be directly used for
Decalcification for the second time processes；
N-th Regeneration Treatment: having collected the waste hydrochloric acid solution after n-th decalcification operation processes, waste hydrochloric acid solution is through filtering
After miscellaneous, adding sulfuric acid solution in waste hydrochloric acid solution, in waste hydrochloric acid solution, calcium ion is 1 with the mol ratio of addition sulfate radical:
0.4-2.3；Regeneration of hydrochloric acid is realized through precipitation, growing the grain, filtration；Hydrochloric acid after regeneration need not it is possible to additionally incorporate hydrochloric acid and can be directly used for
The N+1 time decalcification processes；N is the natural number more than or equal to 2, repeats Regeneration Treatment, until regenerant salt acid solution can not be reprocessed
Till making chitin ash≤3.0%；
The step of described precipitation is addition sulfuric acid solution in the discarded hydrochloric acid after filtering and impurity removing, and mixing speed 20-60 turns every point
Clock, stirring while adding, sulphuric acid added in 30 minutes, after sulphuric acid adds, continues stirring 10-30 minute, makes reaction complete；Described
Growing the grain step is, after precipitation terminates, waste hydrochloric acid and sulfuric acid mixture is stood 1-3 hour, carries out growing the grain process.
Method the most according to claim 1, it is characterised in that the mass concentration of described sulfuric acid solution is 40-98%.
Method the most according to claim 1, it is characterised in that described N is 3,4,5,6,7,8.
Method the most according to claim 1, it is characterised in that the regenerative process as N=5 is: the 1st Regeneration Treatment,
Having collected the waste hydrochloric acid solution after the 1st decalcification operation processes, waste hydrochloric acid solution is after filtering and impurity removing, in waste hydrochloric acid solution
Adding sulfuric acid solution, in waste hydrochloric acid solution, calcium ion is 1:0.4-2.3 with the mol ratio of addition sulfate radical；Through precipitation, growing the grain, mistake
Filter realizes regeneration of hydrochloric acid；Hydrochloric acid after regeneration need not it is possible to additionally incorporate hydrochloric acid and can be directly used for the 2nd decalcification process；
2nd Regeneration Treatment: having collected the waste hydrochloric acid solution after the 2nd decalcification operation processes, waste hydrochloric acid solution is through filtering
After miscellaneous, adding sulfuric acid solution in waste hydrochloric acid solution, in waste hydrochloric acid solution, calcium ion is 1 with the mol ratio of addition sulfate radical:
0.4-2.3；Regeneration of hydrochloric acid is realized through precipitation, growing the grain, filtration；Hydrochloric acid after regeneration need not it is possible to additionally incorporate hydrochloric acid and can be directly used for
3rd decalcification processes；
3rd Regeneration Treatment: having collected the waste hydrochloric acid solution after the 3rd decalcification operation processes, waste hydrochloric acid solution is through filtering
After miscellaneous, adding sulfuric acid solution in waste hydrochloric acid solution, in waste hydrochloric acid solution, calcium ion is 1 with the mol ratio of addition sulfate radical:
0.4-2.3；Regeneration of hydrochloric acid is realized through precipitation, growing the grain, filtration；Hydrochloric acid after regeneration need not it is possible to additionally incorporate hydrochloric acid and can be directly used for
The 4th decalcification processes；
The 4th Regeneration Treatment: having collected the waste hydrochloric acid solution after the 4th decalcification operation processes, waste hydrochloric acid solution is through filtering
After miscellaneous, adding sulfuric acid solution in waste hydrochloric acid solution, in waste hydrochloric acid solution, calcium ion is 1 with the mol ratio of addition sulfate radical:
0.4-2.3；Regeneration of hydrochloric acid is realized through precipitation, growing the grain, filtration；Hydrochloric acid after regeneration need not it is possible to additionally incorporate hydrochloric acid and can be directly used for
The 5th decalcification processes；
The 5th Regeneration Treatment: having collected the waste hydrochloric acid solution after the 5th decalcification operation processes, waste hydrochloric acid solution is through filtering
After miscellaneous, adding sulfuric acid solution in waste hydrochloric acid solution, in waste hydrochloric acid solution, calcium ion is 1 with the mol ratio of addition sulfate radical:
0.4-2.3；Regeneration of hydrochloric acid is realized through precipitation, growing the grain, filtration；Hydrochloric acid after regeneration need not it is possible to additionally incorporate hydrochloric acid and can be directly used for
6th decalcification processes.
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| CA2201212A1 (en) * | 1996-03-27 | 1997-09-27 | Gaston Picard | Process and apparatus for the recovery of chitin |
| CN1467227A (en) * | 2002-07-09 | 2004-01-14 | 邵建华 | Closed path circulation and comprehensive utilization for waste liquor of chitin and derivative production |
| CN101177328A (en) * | 2007-10-26 | 2008-05-14 | 大连利健生物技术开发股份有限公司 | Method for treating waste liquid of chitin and chitosan production |
| CN101974103A (en) * | 2010-11-06 | 2011-02-16 | 扬州日兴生物科技股份有限公司 | Chitin clean production process |
| CN102633402A (en) * | 2011-04-07 | 2012-08-15 | 上海问鼎水处理工程有限公司 | Method for treating chitin waste water |
| CN103665191A (en) * | 2013-12-25 | 2014-03-26 | 嘉兴职业技术学院 | Preparation method of chitosan and immersion device for preparing chitosan |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86106726A (en) * | 1986-09-27 | 1988-04-06 | 中国科学院广州化学研究所 | Production of chitin by stepwise acid process |
| CA2201212A1 (en) * | 1996-03-27 | 1997-09-27 | Gaston Picard | Process and apparatus for the recovery of chitin |
| CN1467227A (en) * | 2002-07-09 | 2004-01-14 | 邵建华 | Closed path circulation and comprehensive utilization for waste liquor of chitin and derivative production |
| CN101177328A (en) * | 2007-10-26 | 2008-05-14 | 大连利健生物技术开发股份有限公司 | Method for treating waste liquid of chitin and chitosan production |
| CN101974103A (en) * | 2010-11-06 | 2011-02-16 | 扬州日兴生物科技股份有限公司 | Chitin clean production process |
| CN102633402A (en) * | 2011-04-07 | 2012-08-15 | 上海问鼎水处理工程有限公司 | Method for treating chitin waste water |
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