CN1101377C - Process for treating waste liquid after recovering cobalt and manganese in process of producing terephthalic acid - Google Patents
Process for treating waste liquid after recovering cobalt and manganese in process of producing terephthalic acid Download PDFInfo
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- CN1101377C CN1101377C CN 00112058 CN00112058A CN1101377C CN 1101377 C CN1101377 C CN 1101377C CN 00112058 CN00112058 CN 00112058 CN 00112058 A CN00112058 A CN 00112058A CN 1101377 C CN1101377 C CN 1101377C
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- acetic acid
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Abstract
The present invention provides a method for treating cobalt-magnesium waste liquid produced by cobalt-magnesium recovery units in the production of p-phthalic acid (PTA), which comprises the following steps: neutralizing the cobalt-magnesium waste liquid with acetic acid produced in PTA production technology; then, evaporating and concentrating the cobalt-magnesium waste liquid by reaction heat released by the oxidizing units of the PTA production technology; cooling the cobalt-magnesium waste liquid to room temperature after being concentrated; after the cobalt-magnesium waste liquid is sufficiently crystallized out of crystals, filtering the cobalt-magnesium waste liquid to separate out sodium acetate trihydrate and sodium benzoate. The method not only avoids discharging waste liquid, but also enables resources to be used, so the unification of an environmental benefit and an economic benefit is obtained.
Description
The present invention relates to from pure terephthalic acid (PTA) produces,, further reclaim the method for sodium-acetate and Sodium Benzoate compound by the discarded liquid that cobalt manganese recovery process is discharged.
When from the by product that PTA produces, reclaiming cobaltous carbonate and manganous carbonate solid mixture, discharge a large amount of waste water solution that contains sodium-acetate and Sodium Benzoate and sodium phthalate and para-phthalic sodium (being called for short the discarded liquid of cobalt manganese), one ton of cobaltous carbonate Mn mixture of average every recovery needs to discharge the discarded liquid 15M of cobalt manganese
3If reclaim the preceding stoste of cobaltous carbonate Mn mixture without concentrating, one ton of cobaltous carbonate manganese product of then every production need be discharged the discarded about 40M of liquid of cobalt manganese
3Its pH value is between the 8.6--9.0, and total sodium salt content is between 30--50%.At present, the production technology of domestic PTA is mainly introduced from the companies such as ICI of U.S. AMOCO company and Mitsui oiling company and Britain.External present treatment process for the PTA by product generally is to adopt burning method or buried method etc.; The domestic progressively absorption method (the employing burning method is also arranged) that then adopts mostly.At home in the existing recovery production technology of each big PTA device, the discarded liquid of cobalt manganese is directly drained into sewage work as a kind of alkaline waste water always, after other alkaline waste water mixes, handle especially by the sewage treatment process that the PTA production system is discharged, average processing costs per ton up to 20 yuan about.In addition, production practical situation from domestic each big PTA device, because its quantity of wastewater effluent is big, and the cobalt metal mn ion that easily causes anerobe to poison that wherein contains a large amount of reluctant organic acid sodium salts and trace, make the production of PTA sewage work be in the overload state operation always, after particularly each PTA factory carried out extending capacity reformation one after another in recent years, the contradiction of sewage disposal was more outstanding.So a large amount of precious resources had both been wasted in the direct discharging of the discarded liquid of cobalt manganese, had increased the load of sewage work again, and make the corresponding rising of cost of reclaiming the cobaltous carbonate manganese product.
In addition, the by product of producing from PTA, reclaim in cobaltous carbonate and the manganous carbonate solid mixture technology, needing to discharge a certain amount of concentration is the dilute acetic acid of 10% (Wt), because its concentration is lower, the trucking costs height, except that factory's periphery a few users needed, redundance all entered Sewage treatment systems.Simultaneously, emit a large amount of reaction heat at the oxidation unit of PTA device, each device all is the method shift reaction heat that adopts the by-product low-pressure steam, the steam of recovery be mainly used in production system companion's heat, heating, and plant area around relevant living facilities.Because after each installed the load raising, the low-pressure steam amount of recovery significantly increased, also have certain surplus behind the device autophage, and low-pressure steam can't be grown the distance conveying.Often, wasted energy with its emptying.
The treatment process that the purpose of this invention is to provide the discarded liquid of a kind of cobalt manganese, not only can from the discarded liquid of cobalt manganese, reclaim out mixtures such as solid sodium-acetate and Sodium Benzoate, and final discharging is to reach directly to enter the neutral water of rain water exhaust system standard, simultaneously, also make original device obtain comprehensive utilization as the part dilute acetic acid and the part by-product low-pressure steam of discharge of wastewater.
Technical scheme of the present invention is as follows:
The treatment process of the discarded liquid of a kind of cobalt manganese, it at first puts into the stainless steel neutralizing well that has agitator with the discarded liquid of cobalt manganese, adds dilute acetic acid under normal temperature, normal pressure, the pH value of regulator solution, to pH value be between the 8.6--8.7.Used 10% dilute acetic acid can utilize and reclaim in cobaltous carbonate and the manganous carbonate solid mixture process dilute acetic acid that gives off (dilute acetic acid of about 10% concentration expressed in percentage by weight).Feed liquid after will neutralizing is then sent in the stainless steel vaporizer of carrying vapour chuck, is heated to boiling state with the low-pressure steam of 0.3Mpa (table), carries out evaporation operation (boiling point is 105 ℃).The vapour phase of evaporation is carried out condensation, cooling, and the composition of its lime set is a water after measured, and pH value is 7, can directly discharge.Used low-pressure steam can be the low-pressure steam that a large amount of reaction heat of utilizing oxidation unit to emit in the PTA Production Flow Chart is produced.
Need the degree Beaume of METHOD FOR CONTINUOUS DETERMINATION feed liquid in the evaporative process, when reaching 26 ° of Be, the expression evaporative process finishes, stops evaporation.
Feed liquid after evaporation concentration is all put into the stainless steel cooling tank of belt stirrer, continuously stirring, naturally cools to the normal temperature state.
The feed liquid that is cooled to behind the normal temperature is carried out suction filtration, and aspiration vacuum level is the 200mm water column.The liquid of extracting out (being called mother liquor) returns feed reservoir and mixes with the discarded liquid of the cobalt manganese of end processing, treats to continue when produce next time to use.White solid after filtration is drained is the mixture of product sodium-acetate and Sodium Benzoate etc.
Advantage of the present invention is: utilize the PTA production technique to reclaim in cobaltous carbonate, the manganous carbonate as the dilute acetic acid of discharge of wastewater and by-product low-pressure steam partly; when being converted into the clean water that can directly discharge as the discarded liquid of the cobalt manganese of sewage discharge always; the a large amount of sodium-acetates and the mixture of Sodium Benzoate have therefrom been isolated again; environment is protected, and resource is fully used.Sodium-acetate and Sodium Benzoate mixture sale price of market are 600 yuan per ton, be no more than 200 yuan (producing the scale estimation of 100 tons of cobaltous carbonate Mn mixtures per year to raise sub-PTA device) and total costs such as the water of product, electricity, vapour consumption and labor wage, equipment amortization, overhead charges are the highest, the compound of one ton of sodium-acetate of every production and Sodium Benzoate consumes 3.2M approximately simultaneously
3Cobalt manganese is discarded liquid, saves more than 60 yuan of sewage disposal expense, and the profit after tax that reclaims product is about 350 yuan per ton.So the compound of recovery sodium-acetate and Sodium Benzoate not only has more significant synthesized environmental protection benefit from the discarded liquid of cobalt manganese, and certain economic benefits is also arranged simultaneously.
The invention will be further described below in conjunction with embodiment:
Embodiment 1: get the discarded liquid 600mL of cobalt manganese, measuring the solution pH value is 9.0.
(1) neutralization:
600mL solution is put into the 1000mL beaker, drip 10% dilute acetic acid while stirring under normal temperature, normal pressure, rate of addition is 30 of per minutes.Simultaneously, the pH value of METHOD FOR CONTINUOUS DETERMINATION solution when pH value becomes 8.6 by 9.0, shows that neutralization reaction finishes.
(2) evaporation:
But the solution after the neutralization is put into the vaporizer of temperature control, under 105 ℃ boiling temperatures, normal pressure, evaporate, concentrate, vaporizer top installs prolong and the logical water coolant of going up additional, and the water vapor that steams is (measuring its pH value is 7) directly discharging after condensation, cooling.Need in the evaporative process constantly to measure the degree Beaume that is concentrated solution, when degree Beaume reaches 26 ° of Be, end evaporation immediately.
(3) cooling, crystallization:
Concentrated solution after the evaporation is put into the beaker of 1000mL, and electric mixer is installed on top, under the situation of continuously stirring, naturally cools to the normal temperature state.
(4) separate:
To be cooled to the mixed liquor of normal temperature, with the B filtration of bleeding, aspiration vacuum level is the 200mm water column.Isolated brown filtrate is mother liquor (wherein contain saturated sodium-acetate and Sodium Benzoate etc., should return feed reservoir during actual production and reuse); White (slightly yellow) solid filter cake is the mixture of sodium-acetate and Sodium Benzoate etc.
This test sodium-acetate and Sodium Benzoate mixture altogether: 128.3g, consume 10% dilute acetic acid 2.2mL, collect water of condensation 372mL, mother liquor 58.5mL.
Embodiment 2: get the discarded liquid 1000mL of alms bowl manganese, measuring the solution pH value is 8.7.
(1) neutralization:
Because of the pH value of solution is 8.7, showing does not wherein have excessive yellow soda ash substantially, need not add acid and carry out neutralization reaction.
(2) evaporation:
But the discarded liquid of 1000mL cobalt manganese is directly put into the vaporizer of temperature control, under 105 ℃ boiling temperature, evaporate in atmospheric pressure state, vaporizer top installs prolong and the logical water coolant of going up additional, and the water vapor that steams is directly discharging (measuring its pH value is 7) after condensation, cooling.When degree Beaume reaches 26 ° of Be, show that evaporative process can finish, and stops evaporation operation at once.
(3) cooling, crystallization:
Concentrated solution after the evaporation is put into the beaker of 2000mL, and a minitype electric mixer is installed on top, and continuously stirring makes it naturally cool to the normal temperature state.
(4) separate:
To be cooled to the mixed liquor of normal temperature, under the vacuum with B 200mm water column, suction filtration.Brown filtrate is mother liquor, wherein contains organic acid sodium salts such as saturated sodium-acetate and Sodium Benzoate, reprocessing again after should returning feed reservoir and the discarded liquid of other cobalt manganese mixing; The filter cake of white (slightly yellow) is the mixture of sodium-acetate and Sodium Benzoate etc.
This test solid mixture material: 358.5g, collect water of condensation 587mL, mother liquor 82mL.Embodiment 3: get the discarded liquid 1500mL of alms bowl manganese, measuring the solution pH value is 8.9.
(1) neutralization:
Stock liquid is put into the beaker of 2000mL, under normal temperature, normal pressure, drip 10% dilute acetic acid while stirring, rate of addition is 30 of per minutes.The pH value of METHOD FOR CONTINUOUS DETERMINATION solution in the dropping process shows that when the pH value of solution is 8.7 neutralization reaction finishes, and stops to add the acid operation immediately.
(2) evaporation:
But the discarded liquid of the cobalt manganese after the neutralization is directly put into the vaporizer of temperature control, under 105 ℃ boiling temperature, evaporate in atmospheric pressure state, vaporizer top installs prolong and the logical water coolant of going up additional, and the water vapor that steams is directly discharging (measuring its pH value is 7) after condensation, cooling.Need the degree Beaume of METHOD FOR CONTINUOUS DETERMINATION solution in the evaporative process, when degree Beaume reaches 26 ° of Be, show that evaporative process can finish, and stops evaporation operation at once.
(3) cooling, crystallization:
Concentrated solution after the evaporation is put into the beaker of 2000mL, and a minitype electric mixer is installed on top, in continuously stirring, makes it naturally cool to the normal temperature state.
(4) separate:
To be cooled to the concentrated mixed liquor of normal temperature state, use B under the vacuum of 200mm water column, suction filtration.Brown filtrate is mother liquor, wherein contains organic acid sodium salts such as saturated sodium-acetate and Sodium Benzoate, and reprocessing again after should returning feed reservoir and the discarded liquid of other cobalt manganese mixing: the filter cake of white (slightly yellow) is the mixture of sodium-acetate and Sodium Benzoate etc.
This test solid mixture material: 478.7g, consume 10% dilute acetic acid 1.8mL, collect water of condensation 1268mL, mother liquor 135mL.
Claims (3)
1. produce in the terephthalic acid technology for one kind, the treatment process of the discarded liquid behind the recovery cobalt manganese, it is characterized in that at first will discarding liquid and add the dilute acetic acid neutralization, making pH value is 8.6～8.7, then evaporation concentration to degree Beaume near 26 ° of Be ', the cooling, filter out sodium-acetate and Sodium Benzoate mixture, mother liquor returns, and mixes with untreated discarded liquid.
2. treatment process according to claim 1, the used dilute acetic acid that it is characterized in that neutralizing are that Production of Terephthalic Acid technology reclaims in carbon vinegar cobalt, the manganous carbonate dilute acetic acid as discharge of wastewater.
3. treatment process according to claim 1 is characterized in that the required heat energy of evaporation concentration is the low-pressure steam of utilizing oxidation unit is emitted in the Production of Terephthalic Acid technology reaction heat to produce.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00112058 CN1101377C (en) | 2000-01-27 | 2000-01-27 | Process for treating waste liquid after recovering cobalt and manganese in process of producing terephthalic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00112058 CN1101377C (en) | 2000-01-27 | 2000-01-27 | Process for treating waste liquid after recovering cobalt and manganese in process of producing terephthalic acid |
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| Publication Number | Publication Date |
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| CN1266049A CN1266049A (en) | 2000-09-13 |
| CN1101377C true CN1101377C (en) | 2003-02-12 |
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| CN 00112058 Expired - Fee Related CN1101377C (en) | 2000-01-27 | 2000-01-27 | Process for treating waste liquid after recovering cobalt and manganese in process of producing terephthalic acid |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408491C (en) * | 2006-07-28 | 2008-08-06 | 沈福昌 | No pollution treatment technique for residue of refined terephthalic acid thin-film evaporator |
| CN101928089B (en) * | 2009-06-26 | 2012-05-30 | 中国石油化工股份有限公司 | Method for disposing antiosmosis thick water out of purified terephthalic acid refined waste water |
| CN110586021B (en) * | 2019-10-09 | 2021-01-15 | 山东省同泰维润食品科技有限公司 | Sodium benzoate waste recycling device |
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