CN101575152B - Reusable method of decanedioic acid phenol-containing wastewater - Google Patents
Reusable method of decanedioic acid phenol-containing wastewater Download PDFInfo
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- CN101575152B CN101575152B CN2008100369716A CN200810036971A CN101575152B CN 101575152 B CN101575152 B CN 101575152B CN 2008100369716 A CN2008100369716 A CN 2008100369716A CN 200810036971 A CN200810036971 A CN 200810036971A CN 101575152 B CN101575152 B CN 101575152B
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Abstract
The invention provides a reusable method of decanedioic acid phenol-containing wastewater, which comprises the following steps: providing decanedioic acid mother liquid which is prepared by neutralizing and acidating and crystallizing a sebacate solution; carrying out solid-liquid separation to the mother liquid to obtain a decanedioic acid solid and first wastewater, reusing the first wastewater,for example, part of the first wastewater is recycled to be used in a neutralization step; neutralizing and extracting balance of the first wastewater, removing phenol, performing pervaporation and r emoving by-product which is sodium sulfate to obtain third wastewater that is recycled to be used in the neutralization step or as flushing water in a centrifugal filtration step or is biologically treated to obtain fourth wastewater satisfying the discharge standard; or laminating the decanedioic acid mother liquid to obtain lower layer dope (part A) which contains crystallized decanedioic acid and upper clear solution (part B); carrying out solid-liquid separation to the lower layer dope (part A) which contains crystallized decanedioic acid to obtain the decanedioic acid solid and the first wastewater; carrying out solid-liquid separation to the upper clear solution (part B) to obtain the decanedioic acid solid and second wastewater; and reusing the first wastewater and the second wastewater.
Description
Technical field
The production technique waste water that the present invention relates to compound recycles method and device thereof, relates to particularly containing the phenol processing wastewater in the sebacic acid production process and recycling method and device thereof.
Background technology
Sebacic acid, English name: Sebacic Acid, another name: sebacic acid, octane dicarboxylic acid, hot dioctyl phthalate, molecular formula: C
10H
18O
4, its structural formula is: HOOC (CH
2)
8COOH character: white flakey or needle crystal.Relative density 1.207 (25 ℃), fusing point 131-134.5 ℃, 294.5 ℃ of boiling points (13.3kPa), specific refractory power 1.442 (133.3 ℃).Industrial goods are white powder or granular, slightly have the lipid acid smell.Be slightly soluble in water, be soluble in organic solvents such as ethanol, ether.
Current, sebacic acid can be used for ester plasticizers such as synthesis of sebacic acid diethyl ester, Uniflex DBS, dinonyl sebacate(DNS), dioctyl sebacate as a kind of more and more important organic synthesis raw material.Also be used to make nylon-610, nylon-1010 and nylon-10 12 etc.It simultaneously also is the intermediate of making polymkeric substance such as polymeric amide, polyester, polyurethane.Also be used to make high temperature grease, tensio-active agent, epoxy curing agent, synthetic flavour and makeup etc.
In Chinese patent application number is 95109421.1 application, disclose a kind of sebacic acid produce in the recycle method of phenol, be in the sebacic acid production process phenolic wastewater by the back crosslinked enhancement type macroporous adsorbent resin carry out adsorption treatment, control absorption flow velocity is 3-4BV/h, and add and put the activated carbon column absorption of winding up, when resin column is adsorbed onto to a certain degree, carrying out desorb handles, desorption and regeneration liquid is after evaporation concentration, directly send back in the cracking still in the sebacic acid production, circulation enters in the sebacic acid production technique as cracking stock.But the weak point of this method is, needs to adopt decolorizing resin, pollutes still comparatively serious during the recovery of resin.
A kind of method that resin is realized the sebacic acid cleaner production of removing of using is disclosed in Chinese patent application 200510038999.X, its process is: in the sebacic acid production technique in sulfuric acid and after contain sebacic acid list sodium salt Zhong Heshui after filtering successively by two groups of adsorption towers, fill a kind of removing resin in every group of adsorption tower, at first remove the colourity in the feed liquid, thinner phenol in the separating and producing again, removal of contamination progressively in process of production, separate purifying substances, reduce the generation that pollutes, thereby substitute traditional end treatment; Adsorb saturated resin and carry out desorption and regeneration, the high density elutriant that desorption gets off is through distilling recyclable phenol, and lower concentration elutriant cover is used for following batch desorption manipulation.Utilize present method can make the sebacic acid quality product reach primary standard, the phenol overwhelming majority in the technology is recyclable, contains the phenol amount in the final waste water of discharging and meets discharging standards.But the weak point of this method is, still must adopt resin, pollutes still comparatively serious in the recovery of resin.
Chinese patent application 02110255.4 relates to a kind of wastewater treatment method, the method for the phenolic wastewater that to be a kind of processing specifically produce in the process of producing sebacic acid.Comprise adjusting, filtration, extraction, dephenolize, five steps of oil removal, after phenolic wastewater removes by filter insolubles, remove the organism in the waste water with higher alcohols as extraction agent and effectively reduce the content of phenol in first extraction section, the load extraction agent removes distillation process, recycle after the higher alcohols back extraction that steams, organism in the waste water reclaims with the form of high boiling material, make extraction agent and phenolic wastewater counter-current extraction in second extraction section with the mixture of phosphoric acid ester and kerosene, recycle after the extraction agent back extraction after saturated, the discharged wastewater met the national standard after the extraction.Can reduce to below the 2.0mg/l by 2000-2500mg/l through counter-current extraction sebacic acid phenolic wastewater phenol content, reach three grades of emission standards of national regulation.But the weak point of this method is that technology is comparatively loaded down with trivial details.
In actual production at present, the technology that the production of common sebacic acid is adopted is usually seen Fig. 1, and this method need be carried out twice decolouring, comprises activated carbon decolorizing and resin decolorization.The deficiency of this method is:
A) water consumption is big, the waste resource
B) wastewater flow rate is big, contaminate environment
C) sebacic acid finished product yield is low, the cost height
D) the sebacic acid final product quality is relatively poor
Because aforementioned production method produces the problem of a large amount of waste water, the production of sebacic acid at present faces increasing environmental protection pressure.
In sum, this area lacks a kind of method that can effectively solve waste water handling problem.Therefore, thus this area presses for a kind of method that water consumption reduces the wastewater treatment expense and reduces wastewater discharge that reduces of developing.
Summary of the invention
Reduce the wastewater treatment expense and reduce wastewater discharge thereby the objective of the invention is to obtain a kind of water consumption that can effectively reduce, solve the method for the waste water handling problem in the sebacic acid production process.
In a first aspect of the present invention, provide a kind of sebacic acid phenolic wastewater to recycle method, it comprises the steps:
The sebacic acid mother liquor is provided, described sebacic acid mother liquor by the sebacate solution that contains phenol neutralize, acidizing crystal obtains;
Described sebacic acid mother liquor carries out solid-liquid separation and obtains the sebacic acid solid and first waste water, and described first waste water recycles, and the described step that recycles comprises:
Resulting part first waste water circulation recovery is used for described neutralization procedure; First waste water of the not cyclic part of surplus neutralizes, and phenol is removed in extraction, the pervaporation step is removed sodium sulfate byproduct, obtain the 3rd waste water, described the 3rd waste water reclaims and is used for the wash-down water of described neutralization procedure, centrifuging step or carries out the 4th waste water that follow-up biochemical treatment must reach emission standard.
Preferably, first waste water recycles 80%-100% (volume) and is used for described neutralization procedure.
Perhaps,
Described sebacic acid mother liquor carries out layering, obtains containing the dope A of the lower floor part and the supernatant liquid B part of crystallization sebacic acid; The wherein said dope A of lower floor that contains the crystallization sebacic acid partly carries out solid-liquid separation, obtains the sebacic acid solid and first waste water; Described supernatant liquid B partly carries out solid-liquid separation, obtains the sebacic acid solid and second waste water; Described first waste water and second waste water recycle, and the described step that recycles comprises:
First waste water and/or second waste water reclamation are used for described acidifying neutralization procedure; Perhaps first waste water and/or second waste water being neutralized, phenol is removed in extraction, the pervaporation step is removed sodium sulfate byproduct, obtain the 3rd waste water, described the 3rd waste water reclaims and is used for the wash-down water of described acidifying neutralization procedure, centrifuging step or carries out the 4th waste water that follow-up biochemical treatment must reach emission standard.
Described waste water recycles step can carry out single recycling or the Combined Cycle use with first waste water, second waste water, the 3rd waste water, the 4th waste water according to practical situation, each waste water that recycles can be whole, it also can be part, preferably, first waste water recycles 80%-100%, second waste water recycles 30%-50%, and three wastes water cycle is used 60%-80%, and the 4th waste water recycles 10%-50%.
In a specific embodiment of the present invention, the described sebacate solution that contains phenol obtains by containing the method that has the following steps: the Viscotrol C raw material obtains the described sebacate solution that contains phenol after being hydrolyzed, adding the phenol cracking.
In a specific embodiment of the present invention, when the described dope A of lower floor that contains the crystallization sebacic acid partly carries out solid-liquid separation, adopt centrifugal filtration process to carry out solid-liquid separation.
In a specific embodiment of the present invention, when described supernatant liquid B partly carries out solid-liquid separation, adopt filtration method to carry out solid-liquid separation.
In a specific embodiment of the present invention, when described sebacic acid mother liquor carried out layering and obtains containing the dope A of the lower floor part of crystallization sebacic acid and supernatant liquid B part, the employing sedimentation was put forward dense method and is carried out layering.
In a specific embodiment of the present invention, when described sebacic acid mother liquor was provided, described sebacic acid mother liquor also carried out activated carbon decolorizing;
Particularly, described activated carbon decolorizing the described sebacate solution that contains phenol carry out in the acidifying and back, acidizing crystal the former two between carry out.
In a specific embodiment of the present invention, resulting sebacic acid solid makes granular or powdery sebacic acid product.
In a specific embodiment of the present invention, resulting sebacic acid solid distills and obtains the purified sebacic acid.
In a specific embodiment of the present invention, described distillation is included in 195～210 ℃, heats up in a steamer the step of removing impurity before carrying out under vacuum tightness 2500～5500 handkerchiefs, and at 180～200 ℃, the sebacic acid distilation steps that carries out under vacuum tightness 80～150 handkerchiefs.
In a specific embodiment of the present invention, described purified sebacic acid carries out granulation, obtains the refining sebacic acid of particulate state.
Description of drawings
Fig. 1 is the technological process of production synoptic diagram of at present existing common sebacic acid;
Fig. 2 is a schematic flow sheet of the present invention; Wherein it comprises layering of sebacic acid mother liquor or not stratified embodiment;
Circuit a is depicted as the not stratified embodiment of sebacic acid mother liquor of the embodiment of the invention 1;
Circuit b is depicted as the stratified embodiment of sebacic acid mother liquor of embodiments of the invention 2;
These flow processs just schematically, are not construed as limiting the invention.
The schematic flow sheet of the embodiment that Fig. 3 combines with the sebacic acid purification step for the present invention.
Embodiment
The present inventor finds through after the extensive and deep research, employing recycles all or part of first waste water, second waste water, the 3rd waste water, the 4th waste water or its combination, can reduce the generation and the discharging of waste water, this method overcome a mass consumption water and the high difficult problem of wastewater treatment expense in the prior art, reached save resource, reduce cost, the purpose of qualified discharge waste water; In a preferred embodiment of the present invention, also adopted sebacic acid has been distilled to carry out the purified scheme, accomplished both to solve environmental issue, reduced cost, improved the effect of sebacic acid quality again, overcome the difficult problem that this area needs to be resolved hurrily always.Finished the present invention on this basis.
Among the present invention, term " contains " or " comprising " represents that various steps or device can be applied in method of the present invention or the equipment together.
Below describe in detail to various aspects of the present invention:
The sebacic acid phenolic wastewater recycles method
The present invention on the basis of the production technique of the common sebacic acid that generally adopts at present with first waste water, second waste water, the 3rd waste water, recycle with the 4th waste water is all or part of, will need the water of interpolation or the wash-down water of centrifuging step to use before the described waste water instead of part neutralization procedure.Described waste water recycles step can be according to practical situation with first waste water, second waste water, the 3rd waste water, carry out single recycling or the Combined Cycle use with the 4th waste water, each waste water that recycles can be whole, also can be part, as long as without limits to goal of the invention of the present invention.
Sebacic acid of the present invention contains the phenol processing wastewater and recycles method, may further comprise the steps:
(a) processing wastewater recycles step:
Before neutralization procedure, with first waste water, second waste water, the 3rd waste water, the 4th waste water is all or part of recycles, the water that instead of part need add uses; The wash-down water that perhaps all or part of the 3rd waste water, the circulation of the 4th waste water is used for the centrifuging step.Described waste water recycles step can carry out single recycling or the Combined Cycle use with first waste water, second waste water, the 3rd waste water, the 4th waste water according to practical situation, each waste water that recycles can be whole, also can be part, as long as without limits to goal of the invention of the present invention.
First waste water: be meant that after the centrifuging step, the contains sodium sulfate of separating and the processing wastewater of phenol comprise the wash-down water that adds in the centrifuging step to sebacic acid mother liquor after the crystallization (not layering or through the lower floor after the layering).
Second waste water: be meant the processing wastewater that supernatant liquid B part obtains through solid-liquid separation after the mother liquor layering is handled, the crystallization sebacic acid content in second waste water lacks than first waste water.Described solid-liquid separation step is preferred, can isolate the small amount of crystalline sebacic acid in the supernatant liquid B part, improves the yield of sebacic acid.
The 3rd waste water: be meant first waste water or/and the part waste water that second waste water produces contains micro-phenol after neutralization extraction, pervaporation step or its combined treatment, can be recycled, also can carry out follow-up biochemical treatment and obtain the 4th waste water.Preferably, first waste water carries out solid-liquid separation before the neutralization extraction, can isolate small amount of crystalline sebacic acid in first waste water, improves yield.
The 4th waste water: be meant that the 3rd waste water carries out the water that obtains after the follow-up biochemical treatment, reach discharging standards, can discharge, also can be recycled, or be used for producing as water coolant etc., also can purify the back and use, for example be used as wash-down water etc., only otherwise goal of the invention of the present invention is produced restriction to get final product as ortho-water.
(b) sebacic acid mother liquor layering treatment step (preferred steps):
Carry in the dense process in the final step sedimentation of original production process acidizing crystal step the sebacic acid mother liquor be divided into two layers up and down:
Partly for containing the dope of crystallization sebacic acid, after solid-liquid separation, the solid product that obtains is the common sebacic acid of work in-process to the dope A of lower floor that obtains, and the product liquid that obtains is first waste water;
Partly for containing the clear liquid of a small amount of suspension crystallization sebacic acid, after solid-liquid separation, the solid product that obtains is the common sebacic acid of work in-process to the supernatant liquid B that obtains, and the product liquid that obtains is second waste water.
(c) treatment step (preferred steps) of first waste water, second waste water or its combination
With first waste water, second waste water or its combination that does not recycle neutralize extraction, pervaporation step or its combined treatment, obtain the 3rd waste water.More preferably, first waste water carries out solid-liquid separation before the neutralization extraction, can isolate small amount of crystalline sebacic acid in first waste water, improves yield.
(d) treatment step of the 3rd waste water (preferred steps)
The 3rd waste water that does not recycle is carried out obtaining the 4th waste water after the biochemical treatment, reach discharging standards, can discharge, also can be used as water coolant, the preceding water that needs interpolation of neutralization procedure etc. is used for producing, also can purify the back uses as ortho-water, for example be used as wash-down water etc., only otherwise goal of the invention of the present invention is produced restriction to get final product.
(e) under the constant situation of original production system, can only adopt activated carbon decolorizing, remove the resin decolorization step in the original production process, preferably remove the resin decolorization step.
Processing wastewater of the present invention recycles method and is not limited to above-mentioned steps, those skilled in the art are according to having known technology can make up other in each step the step that recycles now, as long as this recycles step to goal of the invention of the present invention without limits.
Sebacic acid of the present invention contains the phenol processing wastewater and recycles in the method, usually the water that needs before the processing wastewater instead of part neutralization procedure that recycles to add is used or is used for the wash-down water of centrifuging step.Certainly, those skilled in the art can further adjust according to the needs of producing, as long as this is adjusted to goal of the invention of the present invention without limits.
Among the present invention, the processing wastewater that is used to recycle is not specifically limited, can be with the every processing wastewater that produces in the sebacic acid production technique, but first waste water is more because contain the crystallization sebacic acid, more worth recycling.
Below sebacic acid contained each step that the phenol processing wastewater recycles method describe in detail.
First waste water recycles step: recycle first waste water is all or part of, the water that needs before the instead of part neutralization procedure to add uses.Because it is more that first waste water contains the crystallization sebacic acid, more worth recycling.
Second waste water recycles step: recycle second waste water is all or part of, the water that needs before the instead of part neutralization procedure to add uses, and can further reduce the consumption of water.
Three wastes water cycle is used step: recycle the 3rd waste water is all or part of, need the water that adds or the wash-down water of centrifuging step to use before the instead of part neutralization procedure, can further reduce the consumption of water.
The 4th waste water uses step: owing to meet discharging standards, can directly discharge, also can be recycled, or be used for producing as water coolant etc., also can purify the back and use, for example be used as wash-down water etc., only otherwise goal of the invention of the present invention is produced restriction to get final product as ortho-water.
Described waste water recycles step can carry out single recycling or the Combined Cycle use with first waste water, second waste water, the 3rd waste water, the 4th waste water according to practical situation, each wastewater flow rate that recycles can determine according to practical situation, both can be whole, also can be part, as long as without limits to goal of the invention of the present invention.First waste water is more because contain the crystallization sebacic acid, more worth recycling.
Usually, those skilled in the art think that the wastewater flow rate that produces in the production process of sebacic acid is big, and make wastewater treatment costly, make environmental issue be difficult to effective solution; And the present inventor is surprised to find, the water that needs in taking processing wastewater partly replaced and before the operation to add uses or is used for the wash-down water of centrifuging step, and in conjunction with other corresponding technology, can reduce the consumption of water, thereby reduce the discharging of waste water, the wastewater flow rate of need neutralize extraction and pervaporation processing is significantly reduced, greatly reduce the wastewater treatment expense, and reach the qualified discharging of waste water; Because wastewater flow rate is little, phenol and sodium sulfate concentration height in the waste water, so recovery value is big, cost recovery is low, makes wastewater treatment become lucrative, as to have an economic benefit thing.Above-mentioned discovery has solved the environmental issue that this area exists always, has social benefit widely.
Preferably, the described step that recycles also comprises and with carrying in the final step sedimentation of original production process acidizing crystal step in the dense process sebacic acid mother liquor is divided into two layers up and down:
Partly for containing the dope of crystallization sebacic acid, after solid-liquid separation, the solid product that obtains is the common sebacic acid of work in-process to the dope A of lower floor that obtains, and obtaining product liquid is first waste water;
Partly for containing the clear liquid of a small amount of suspension crystallization sebacic acid, after solid-liquid separation, the solid product that obtains is the common sebacic acid of work in-process to the supernatant liquid B that obtains, and the product liquid that obtains is second waste water.
Described stratified ratio is not specifically limited, only otherwise goal of the invention of the present invention is produced restriction to get final product.
The method of described solid-liquid separation is not specifically limited, only otherwise goal of the invention of the present invention is produced restriction to get final product.Can adopt the traditional solid-liquid separating method in this area to carry out.
Preferably, the upper strata mother liquor adopts filter method to carry out solid-liquid separation.
Preferably, lower floor's mother liquor adopts centrifugal filtering method to carry out solid-liquid separation.
Preferably, with first waste water, second waste water or its combination that does not recycle neutralize extraction, pervaporation step or its combined treatment, obtain the 3rd waste water.More preferably, first waste water carries out solid-liquid separation before the neutralization extraction.The advantage of described treatment step:
1) can isolate small amount of crystalline sebacic acid in first waste water, improve yield.
2) can extract phenol and sodium sulfate, the phenol of extraction can be used as raw material and uses, and the sodium sulfate of extraction can be sold, and recovery value is arranged;
3) only contain micro-phenol in the 3rd waste water, contains sodium sulfate can reduce the amount that recycles the sodium sulfate in the Production Flow Chart hardly; Just do not recycle if second waste water is treated, phenol and sodium sulfate are cumulative in Production Flow Chart, and production can't normally be carried out;
4) in the 3rd waste water because contains sodium sulfate not can be carried out subsequent disposal, as biochemical treatment, the micro-phenol in the 3rd waste water of degrading obtains the 4th waste water, makes it reach national specified discharge standard.
Preferably, the 3rd waste water that does not recycle is carried out obtaining the 4th waste water after the biochemical treatment, reach discharging standards, can discharge, also can be recycled, or be used for producing, also can purify the back and use as ortho-water as water coolant etc., for example be used as wash-down water etc., only otherwise goal of the invention of the present invention is produced restriction to get final product.
More preferably, under the constant situation of original production system, can only adopt activated carbon decolorizing, remove the resin decolorization step in the original production process, the described resin decolorization step of removing is preferred, can reduce because of what macroporous resin regeneration was produced and contain a large amount of waste water such as phenol, alkali, acidic substance, reduce production cost, reduce corresponding wastewater treatment expense and quantity discharged; Can reduce simultaneously the material equipment investment.Though macroporous resin plays certain adsorption to organic pigment, phenol, lipid acid etc. in sebacic acid production, a large amount of waste water that it is produced in regenerative process cause great pollution to environment.Adopt activated carbon decolorizing because of its disposable use, do not produce secondary pollution, exhausted gac professional production producer can also reclaim the back regeneration.
For example, in a concrete embodiment, a kind of sebacic acid phenolic wastewater recycles method, and it comprises the steps:
The sebacic acid mother liquor is provided, described sebacic acid mother liquor by the sebacate solution that contains phenol neutralize, acidizing crystal obtains;
Described sebacic acid mother liquor carries out layering, obtains containing the dope A of the lower floor part and the supernatant liquid B part of crystallization sebacic acid; The wherein said dope A of lower floor that contains the crystallization sebacic acid partly carries out solid-liquid separation, obtains the sebacic acid solid and first waste water; Described supernatant liquid B partly carries out solid-liquid separation, obtains the sebacic acid solid and second waste water; Described first waste water and second waste water recycle, and the described step that recycles comprises:
First waste water and/or second waste water reclamation are used for described neutralization procedure; Perhaps first waste water and/or second waste water being neutralized, phenol is removed in extraction, the pervaporation step is removed sodium sulfate byproduct, obtain the 3rd waste water, described the 3rd waste water reclaims and is used for the wash-down water of described neutralization procedure, centrifuging step or carries out the 4th waste water that follow-up biochemical treatment must reach emission standard.
More preferably, described waste water recycles step can be according to practical situation with first waste water, second waste water, the 3rd waste water, the 4th waste water carries out single recycling or the Combined Cycle use, and each waste water that recycles can be whole, also can be part.
More preferably, when described sebacic acid mother liquor carries out layering and obtains containing the dope A of the lower floor part of crystallization sebacic acid and supernatant liquid B part, carry in sedimentation and to carry out natural layering on the dense basis.
Stratified ratio is not specifically limited, even can be not stratified.Under not stratified situation, described sebacic acid mother liquor carries out solid-liquid separation and obtains the sebacic acid solid and first waste water, and described first waste water recycles, and the described step that recycles comprises: resulting first waste water circulation recovery is used for described neutralization procedure; First waste water of the not cyclic part of surplus neutralizes, and phenol is removed in extraction, the pervaporation step is removed sodium sulfate byproduct, obtain the 3rd waste water, described three wastes water cycle reclaims and is used for the wash-down water of described neutralization procedure, centrifuging step or carries out the 4th waste water that follow-up biochemical treatment must reach emission standard;
More preferably, when the described dope A of lower floor that contains the crystallization sebacic acid partly carries out solid-liquid separation, adopt centrifugal filtration process to carry out solid-liquid separation.
More preferably, when described supernatant liquid B partly carries out solid-liquid separation, adopt filtration method to carry out solid-liquid separation.
More preferably, under the constant situation of original production system, can only adopt activated carbon decolorizing, remove the resin decolorization step in the original production process.
More preferably, resulting sebacic acid can distill and obtain the purified sebacic acid.Particularly for example, described distillation is included in 195～210 ℃, heats up in a steamer the step of removing impurity before carrying out under vacuum tightness 2500～5500 handkerchiefs, and at 180～200 ℃, the sebacic acid distilation steps that carries out under vacuum tightness 80～150 handkerchiefs.
In a concrete embodiment, described purified sebacic acid carries out granulation, obtains the refining sebacic acid of particulate state.
The contriver finds that described mother liquor layering treatment step has following advantage:
1) through described stratification step, the content of phenol and sodium sulfate is higher than first waste water in second waste water that obtains, and the content of crystallization sebacic acid is lower than first waste water, makes the waste water that recycles that better choice arranged.
2) can preferably first waste water all be recycled, correspondingly reduce the amount of recycling of second waste water, improve the sebacic acid yield;
3) if process water all recycles, phenol and sodium sulfate can't be discharged, and is cumulative in Production Flow Chart, and production can't normally be carried out.Owing to reduced the amount of recycling of second waste water, can make phenol and sodium sulfate discharge Production Flow Chart with second waste water that does not recycle more.
Equipment
The equipment that the present invention can adopt traditional sebacic acid production technology to adopt, comprise hydrolysis unit, cracking unit, neutralisation unit, activated carbon decolorizing unit, resin decolorization unit, acidizing crystal unit, centrifuging unit, melt the unit, granulation unit, drying unit, in and the equipment of extraction cells etc.
The specific embodiment of the present invention, equipment including, but not limited to hydrolysis unit, cracking unit, neutralisation unit, activated carbon decolorizing, acidizing crystal unit, centrifuging unit, in and extraction cells etc., pervaporation module, biochemical treatment unit, waste water recycle the equipment of unit etc.The sebacic acid that is used for of the present invention contains the phenol processing wastewater and recycles unitary equipment, including, but not limited to equipment such as pipeline, storage tank, equipment for separating liquid from solid.
Related equipment of the present invention is not specifically limited, and can adopt this area equipment commonly used, only otherwise goal of the invention of the present invention is produced restriction to get final product.
Major advantage of the present invention is as follows:
1) reduces water consumption, save resource
2) reduce wastewater discharge, reduce cost for wastewater treatment
3) in a preferred implementation, the resin operation be can reduce, cost of investment and production cost reduced
4) improve sebacic acid mother liquor and need sodium sulfate in neutralization extraction, the pervaporation processing wastewater and the concentration of phenol, improved recovery value
5) improve sebacic acid finished product yield, reduce cost
6) the present invention can " a kind of sebacic acid purified method " be used in combination, improves the sebacic acid quality with another invention of the inventor.
Other aspects of the present invention are because the disclosure of this paper is conspicuous to those skilled in the art.
Below in conjunction with specific embodiment, further set forth the present invention.The data that should be understood that these embodiment and mention only are used to the present invention is described and are not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, or carries out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all umbers are weight part, and all per-cents are weight percentage.
Unless otherwise defined or explanation, same meanings of being familiar with of all specialties used herein and scientific words and those skilled in the art.Any in addition method similar or impartial to described content and material all can be applicable in the inventive method.
Embodiment 1
Shown in the route a of Fig. 2, raw material Viscotrol C, zinc oxide, water raw material obtain containing the sebacate solution of phenol through hydrolysis, cracking.Sebacate solution neutralizes, activated carbon decolorizing, acidizing crystal, obtains the sebacic acid mother liquor.Contain 4% sebacic acid of having an appointment in the sebacic acid mother liquor.
Described sebacic acid mother liquor carries out the solid-liquid filtration and obtains the sebacic acid solid and first waste water, and described first waste water recycles:
First waste water circulation recovery of resulting 60 weight % is used for described neutralization procedure; First waste water of the not cyclic part of surplus 40% neutralizes, and phenol is removed in extraction, the pervaporation step is removed sodium sulfate byproduct, obtains the 3rd waste water, and described the 3rd waste water reclaims and is used to carry out the 4th waste water that follow-up biochemical treatment must reach emission standard.
Described first waste water, the 3rd waste water, the 4th waste water composed as follows:
Impurity such as sodium sulfate sebacic acid phenol glycerin, lipid acid
The composition of first waste water: 6-16% 0.3-0.5% 1500-4000PPM is a small amount of
The composition of the 3rd waste water: 00 200PPM trace
The composition of the 4th waste water: the following trace of 00 0.5PPM
(annotate: aforementioned proportion is part by weight)
As shown in Figure 2, the subsequent disposal of the common sebacic acid of work in-process has multiple choices among the figure, such as:
1) fusing, granulation obtain the granulated common sebacic acid
2) drying obtains the common sebacic acid of powdery
3) process for purification of employing sebacic acid obtains refining sebacic acid.
4) adopt additive method to obtain the finished product sebacic acid
Comparative Examples 1
Fig. 1 is existing technology (Comparative Examples 1), it adopts the step identical with embodiment 1, difference is, Comparative Examples 1 does not recycle described part first waste water, employing resin decolorization step, and first waste water that adopts filtration, neutralization extraction and pervaporation processing not to recycle part obtains the 3rd waste water and the 3rd waste water is carried out biochemical treatment.
Embodiment 1 compares with the route of Comparative Examples 1:
Recycle owing to phenolic wastewater among the embodiment 1, the concentration of the phenol in the water in the technological process of production has improved, the phenol that neutralization extracts is more than prior art, therefore producing 1 ton of sebacic acid is 50KG with the phenol amount, and the scheme of Comparative Examples 1 is 70KG with the phenol amount, so the scheme of embodiment 1 reduces the consumption 20KG of phenol.
Therefore embodiment 1 compares with Comparative Examples 1 and obtains sebacic acid 35-40KG more because waste water recycles, and a part of sebacic acid in the waste water has obtained recovery.2 tons in reclaim(ed) sulfuric acid sodium.
Adopting 1 ton of sebacic acid water consumption of scheme production of embodiment 1 is 15 tons, and adopts 40 tons of the scheme waters shown in the Comparative Examples 1 (Fig. 1), therefore adopts method of the present invention to conserve water 25 tons, and 15 tons of the 4th wastewater flow rates of discharging reduce 25 tons of waste water of discharging.The 4th waste water reaches discharging standards (former technology exceed standard discharging).
Embodiment 2
Shown in the route b among Fig. 2, the method of embodiment 2 is with reference to embodiment 1, and difference is: adopt sebacic acid mother liquor stratification step, described whole first waste water and part three wastes water cycle are used, adopt neutralization extraction and pervaporation to handle second waste water and obtain the 3rd waste water, specific as follows:
The sebacic acid mother liquor divides stratum proportion: upper strata 50%, lower floor 50%.
The recycle of first waste water: 100% of first waste water is recycled, be used for the water use that described neutralization procedure former generation adds for part;
The recycle of the 3rd waste water: 60% of the 3rd waste water is recycled, be used for described neutralization procedure former generation and use for the water of part interpolation and the wash-down water of centrifuging step;
(annotate: aforementioned proportion is part by weight)
Impurity such as sodium sulfate sebacic acid phenol glycerin, lipid acid
The composition of first waste water: 6-16% 0.3-0.5% 1500-4000PPM is a small amount of
The composition of second waste water: 6-16% 0.25-0.35% 1500-4000PPM is a small amount of
The composition of the 3rd waste water: 00 200PPM trace
The composition of the 4th waste water: the following trace of 00 0.5PPM
(annotate: aforementioned proportion is part by weight)
Producing 1 ton of sebacic acid water consumption is 5 tons, and 40 tons of scheme waters shown in Figure 1,35 tons of the amounts of conserving water, and 5 tons of the 4th wastewater flow rates of discharging reduce by 35 tons of waste water, and the 4th waste water reaches discharging standards (former technology exceed standard discharging).
Because the phenolic wastewater that recycles is more than embodiment 1, the concentration ratio embodiment 1 of the phenol in the water in the technological process of production further improves, the phenol that neutralization extracts is more, therefore producing 1 ton of sebacic acid is 35KG with the phenol amount, and prior art scheme (also being Fig. 1 scheme) is 70KG with the phenol amount, reduces the consumption 35KG of phenol.
Because the phenolic wastewater that recycles is more than embodiment 1, therefore the sebacic acid in the waste water of recovery obtains sebacic acid 40-45KG than embodiment more than 1 more.
2 tons in reclaim(ed) sulfuric acid sodium.
Embodiment 3
The method of embodiment 3 is with reference to embodiment 2, and difference is: combine with the process for purification of sebacic acid.Its flow process is seen Fig. 3.
Specific as follows:
The sebacic acid mother liquor divides stratum proportion: upper strata 50%, lower floor 50%.
The recycle of first waste water: 100% of first waste water is recycled, be used for the water use that described neutralization procedure former generation adds for part;
The recycle of the 3rd waste water: 60% of the 3rd waste water is recycled, be used for described neutralization procedure former generation and use for the water of part interpolation and the wash-down water of centrifuging step;
The process for purification of sebacic acid is as follows: described common sebacic acid work in-process distill, described distillation is included in 195～210 ℃, heat up in a steamer the step of removing impurity before carrying out under vacuum tightness 2500～5500 handkerchiefs, and at 180～200 ℃, the sebacic acid distilation steps that carries out under vacuum tightness 80～150 handkerchiefs obtains described purified sebacic acid.
Producing 1 ton of sebacic acid water consumption is 5 tons, and 40 tons of prior art scheme waters, 35 tons of the amounts of conserving water, and 5 tons of the 4th wastewater flow rates of discharging reduce by 35 tons of waste water, and the 4th waste water reaches discharging standards (former technology exceed standard discharging).
Because the phenolic wastewater that recycles is more than embodiment 1, the concentration ratio embodiment of the phenol in the water in the technological process of production further improves, the phenol that neutralization extracts is more than prior art, therefore producing 1 ton of sebacic acid is 35KG with the phenol amount, and prior art scheme (Fig. 1 scheme) is 70KG with the phenol amount, reduces the consumption 35KG of phenol.
Because the phenolic wastewater that recycles is more than embodiment 1, therefore the sebacic acid in the waste water of recovery obtains sebacic acid 40-45KG than embodiment more than 1 more.
2 tons in reclaim(ed) sulfuric acid sodium.
Finished product reaches refining sebacic acid quality level.
The comparison of the sebacic acid that the sebacic acid that Fig. 1 obtains (the also common sebacic acid production technology that promptly generally adopts at present) and the embodiment of the invention 3 obtain:
(1) the two the sebacic acid quality that obtains and the comparison of yield
Technology the present invention (embodiment 3) at present
The common sebacic acid quality of sebacic acid quality, relatively poor refining sebacic acid quality is good
The sebacic acid yield is lower, and about 50% is higher, and about 52%
The sebacic acid cost is higher lower
Described " common sebacic acid quality " is meant:
Content is more than 99.5%
Look number (the molten APHA of alkali) is below 15
Ash content is below 0.03%
Fusing point 131-134.5 ℃
Moisture is below 0.3%
Neutralization value: more than 552
Described " refining sebacic acid quality " is meant:
Content is more than 99.5%
Look number (the molten APHA of alkali) is below 5
Ash content is below 0.005%
Fusing point is more than 132 ℃
Moisture is below 0.05%
Neutralization value: more than 553
(2) the two environmental protection cost relatively
Technology the present invention (embodiment 3) at present
Can reach discharging standards: can not energy
The water consumption of saving: (to produce 1 ton of sebacic acid) about 35 tons
Content of phenol in waster: below about 200PPM 0.5PPM
Waste water sodium sulphate content: 6-8% 0
The sodium sulfate that reclaims: about 2 tons
Cost for wastewater treatment: just
All documents of mentioning are in this manual all quoted as a reference in this application.Should be understood that in addition after having read foregoing of the present invention, those skilled in the art can make various changes or modifications the present invention, these equivalent form of values fall within the application's the scope equally.
Claims (10)
1. a sebacic acid phenolic wastewater recycles method, and it comprises the steps:
The sebacic acid mother liquor is provided, described sebacic acid mother liquor by the sebacate solution that contains phenol neutralize, acidizing crystal obtains;
Described sebacic acid mother liquor is carried out solid-liquid separation obtain the sebacic acid solid and first waste water, described first waste water is recycled, the described step that recycles comprises:
Resulting part first waste water circulation recovery is used for described neutralization procedure; First waste water of the not cyclic part of surplus neutralizes, and phenol is removed in extraction, the pervaporation step is removed sodium sulfate byproduct, obtain the 3rd waste water, described the 3rd waste water reclaims and is used for the wash-down water of described neutralization procedure, solid-liquid separation step or carries out the 4th waste water that follow-up biochemical treatment must reach emission standard;
Perhaps,
Described sebacic acid mother liquor is carried out layering, obtain containing the dope A of the lower floor part and the supernatant liquid B part of crystallization sebacic acid; The wherein said dope A of lower floor that contains the crystallization sebacic acid partly carries out solid-liquid separation, obtains the sebacic acid solid and first waste water; Described supernatant liquid B partly carries out solid-liquid separation, obtains the sebacic acid solid and second waste water; Described first waste water and second waste water are recycled, and the described step that recycles comprises:
First waste water and/or second waste water reclamation are used for described neutralization procedure; Perhaps first waste water and/or second waste water being neutralized, phenol is removed in extraction, the pervaporation step is removed sodium sulfate byproduct, obtain the 3rd waste water, described the 3rd waste water reclaims and is used for the wash-down water of described neutralization procedure, solid-liquid separation step or carries out the 4th waste water that follow-up biochemical treatment must reach emission standard.
2. the method for claim 1 is characterized in that, the described sebacate solution that contains phenol obtains by containing the method that has the following steps: obtain the described sebacate solution that contains phenol after the Viscotrol C raw material is hydrolyzed, adds the phenol cracking.
3. the method for claim 1 is characterized in that, when the described dope A of lower floor that contains the crystallization sebacic acid is partly carried out solid-liquid separation, adopts centrifugal filtration process to carry out solid-liquid separation.
4. the method for claim 1 is characterized in that, when described supernatant liquid B is partly carried out solid-liquid separation, adopts filtration method to carry out solid-liquid separation.
5. the method for claim 1 is characterized in that, when described sebacic acid mother liquor was carried out layering and obtains containing the dope A of the lower floor part of crystallization sebacic acid and supernatant liquid B part, the employing sedimentation was put forward dense method and carried out layering.
6. the method for claim 1 is characterized in that, when described sebacic acid mother liquor is provided, described sebacic acid mother liquor is also carried out activated carbon decolorizing, and described activated carbon decolorizing carries out before the described sebacate solution that contains phenol neutralizes back, acidizing crystal.
7. the method for claim 1 is characterized in that, makes resulting sebacic acid solid granular or powdery sebacic acid product.
8. the method for claim 1 is characterized in that, resulting sebacic acid solid is distilled obtain the purified sebacic acid.
9. method as claimed in claim 8, it is characterized in that described distillation is included in 195～210 ℃, heat up in a steamer the step of removing impurity before carrying out under vacuum tightness 2500～5500 handkerchiefs, and at 180～200 ℃, the sebacic acid distilation steps that carries out under vacuum tightness 80～150 handkerchiefs.
10. method as claimed in claim 8 is characterized in that, described purified sebacic acid is carried out granulation, obtains the refining sebacic acid of particulate state.
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| CN102351357B (en) * | 2011-06-24 | 2012-10-17 | 扬州大学 | Resource utilization of waste water containing phenol and sodium sulfate and treating method |
| CN102311195B (en) * | 2011-06-24 | 2012-08-29 | 扬州大学 | Recycling utilization and processing method for wastewater generated in sebacic acid production process |
| CN102372378A (en) * | 2011-10-10 | 2012-03-14 | 山东天兴生物科技有限公司 | Treatment method of waste water produced by adopting castor oil to prepare decanedioic acid |
| CN102491561B (en) * | 2011-12-19 | 2013-06-05 | 山西宏远科技股份有限公司 | Method and device for treating process waste water produced by fatty acid production |
| CN104609640B (en) * | 2013-11-05 | 2017-02-15 | 中蓝连海设计研究院 | Comprehensive treatment method of sebacic acid production wastewater |
| CN104609641B (en) * | 2013-11-05 | 2017-02-15 | 中蓝连海设计研究院 | Sebacic acid wastewater evaporative desalination pretreatment method |
| CN103936216A (en) * | 2014-03-14 | 2014-07-23 | 湖南化工研究院 | Polycarbonate process wastewater treatment method |
| CN104496099B (en) * | 2014-11-19 | 2016-08-24 | 华东理工大学 | Sodium sulfate wastewater method of comprehensive utilization in coal tar processing and device |
| CN109336330B (en) * | 2018-11-13 | 2022-02-08 | 彤程化学（中国）有限公司 | Efficient treatment method of rubber accelerator wastewater |
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