CN104418723B - The recovery method of trade effluent dilute formic acid and device - Google Patents
The recovery method of trade effluent dilute formic acid and device Download PDFInfo
- Publication number
- CN104418723B CN104418723B CN201310362587.6A CN201310362587A CN104418723B CN 104418723 B CN104418723 B CN 104418723B CN 201310362587 A CN201310362587 A CN 201310362587A CN 104418723 B CN104418723 B CN 104418723B
- Authority
- CN
- China
- Prior art keywords
- formic acid
- phosphoric acid
- dilute
- acid
- kettle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
The invention discloses a kind of recovery method and device of trade effluent dilute formic acid, it solve the problems such as too high, the direct exhaust emission environment of existing dilute formic acid concentrated cost, it is characterized in that: adopt the waste water reclaiming device be made up of storage still (7), water suction tower (8), filler (9), shower nozzle (10), condenser (12), storagetank (16), Crude product input valve (17), heating medium inlet valve (18), dehydrating kettle (19), recycle pump (20) etc. to carry out the dense formic acid product of phosphoric acid circulation concentration and recovery in trade effluent containing a large amount of dilute formic acid.There is technique advanced person, in conjunction with advantages such as reasonable, easy to operate, preventing pollution, can be widely used in Chemical Manufacture enterprise and carry out dewatering and recovery to the waste water produced containing a large amount of dilute formic acid, it is applied and will bring abundant economic benefit for enterprise.
Description
Technical field
The invention belongs to sewage water treatment method, especially relate to a kind of dilute formic acid to producing in Production in Chemical Plant process and adopt phosphoric acid circulation concentration technology to carry out recovery method and the device of trade effluent dilute formic acid.
Background technology
Formic acid, also known as making formic acid, molecular formula is HCOOH, colourless and have pungent odour, and is corrosive, redness of bubbling after human skin contact.Formic acid is important industrial chemicals and solvent, is widely used in the industry such as agricultural chemicals, leather, dyestuff, medicine and rubber.In above-mentioned commercial run, produce a large amount of dilute formic acid solution.Because the boiling-point difference of formic acid and water only has 0.7 DEG C, and form constant boiling point with water, so be difficult to concentrated dilute formic acid with conventional rectificating method.How concentrating dilute formic acid, existing way is a lot.As patent of invention " apparatus and method of intermittent azeotropic rectifying method purifying formic acid solution ", CN101596371A, is permitted pine forest etc.Its main thought makees entrainer for first adopting hexanaphthene, is that the dilute formic acid aqueous solution initial concentration of 10% is to 30% by mass concentration; Re-use chlorobenzene and make entrainment agent, the azeotrope of tower top first constantly extraction chlorobenzene and water, the mixing composition of extraction chlorobenzene-formic acid-water when tower top temperature is at 95 DEG C ~ 102 DEG C, after phase-splitting, the massfraction of formic acid can reach 60% ~ 70%; Finally use compression rectification, control pressure is at 4atm, and tower reactor can reach the concentration formic acid and high solution of about 80 ~ 85%; And for example patent of invention " novel method that a kind of formic acid is purified ", CN101391945A, Ding Chengrong etc.Its thinking is the water sloughed with Calcium Chloride Powder Anhydrous in formic acid, and then distillation obtains concentration formic acid and high.But this two schemes, cost of equipment is large, inferior separating effect, and the latter's manual operation expense is large, and has acid mist pollution environment.Above-mentioned similar technique only has a small amount of production application, does not all promote, and causes on market and has a large amount of dilute formic acid supply, cheap.Dilute formic acid is made direct discharging of waste water by some chemical enterprises, causes environmental pollution.
Summary of the invention
Object of the present invention will solve the problems of the technologies described above exactly, for chemical enterprise provide a kind of equipment simple, invest little, yield is high, continuous seepage, easy to operate use Phosphoric Acid Concentration technique is to the recovery method of trade effluent dilute formic acid and device.
Technical scheme of the present invention is: the technical process that phosphoric acid circulation concentrates dilute formic acid is as follows
(1) adopt thermal dehydration still, remove the moisture content in dilute phosphoric acid, obtain thick polyphosphoric acid and high-concentration phosphoric acid;
(2) allow thick polyphosphoric acid and high-concentration phosphoric acid dirty along packing layer in water suction tower, after absorbing moisture content, become dilute phosphoric acid gradually, then flow to dilute phosphoric acid storage still;
(3) with pump, dilute phosphoric acid is sent into dehydrating kettle, realize phosphoric acid circulation and utilize.
(4) adopt evaporating kettle evaporation formic acid solution, obtain the dilute formic acid steam that mass concentration is 20 ~ 80%;
(5) formic acid vapor is allowed first by cold filling layer above evaporating kettle or the packing layer that has charging dilute formic acid solution dirty, solid entrainment in removing formic acid vapor;
(6) by there being the water suction tower of thick polyphosphoric acid and the dirty packing layer of high-concentration phosphoric acid, the most of moisture content in removing formic acid vapor;
(7) formic acid vapor after concentrating becomes concentration formic acid and high liquid by condensing tube condensation.
A kind of dilute formic acid solution recovery device, it is by evaporating kettle, water suction tower, part such as storage still and condenser etc. is formed, filler and feed valve is established above evaporating kettle, water suction tower is arranged at above evaporating kettle, bottom is stored still respectively by pipeline with evaporating kettle and phosphoric acid and is connected, filler is established in inside, shower nozzle is established at top, top arranges dehydrating kettle, bottom dehydrating kettle, leakage fluid dram is set, be connected with shower nozzle by the pipeline of band phosphoric acid valve, water suction tower side sets out steam ports near tower top place, be connected by the steam inlet of pipeline with the prolong in condenser, the exit end of prolong is communicated with formic acid storagetank by the pipeline of carries product valve, storage still bottom discharge port arranges Phosphoric Acid Circulating Pump, bottom in its inlet pipe access phosphoric acid storage still, outlet pipe inserts in dehydrating kettle, dehydrating kettle upper side wall arranges Crude product input valve, lower wall arranges heating medium inlet valve.
Beneficial effect of the present invention is: owing to adopting phosphoric acid circulation technique, absorb moisture content by phosphoric acid to concentrate dilute formic acid, realize the process of trade effluent comprehensive purifying, not only rational in infrastructure, three-waste free discharge, but also can operate continuously, can be widely used in Chemical Manufacture enterprise and carry out dewatering and recovery to the waste water produced containing a large amount of dilute formic acid, it is applied and will bring abundant economic benefit for enterprise.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention
In figure: 1 is evaporating kettle, 2 is valve of slagging tap, and 3 is bleeder valve, and 4 is feed valve, 5 is steam valve, and 6 is pipeline, and 7 is storage still, and 8 is water suction tower, 9 is filler, and 10 is shower nozzle, and 11 is phosphoric acid valve, and 12 is condenser, 13 is prolong, and 14 is water intaking valve, and 15 is product valve, 16 is storagetank, and 17 is Crude product input valve, and 18 is heating medium inlet valve, 19 is dehydrating kettle, and 20 is recycle pump, and 21 is filler.
Embodiment
As shown in Figure 1, the retrieving arrangement of trade effluent dilute formic acid, it is by evaporating kettle 1, water suction tower 8, part such as storage still 7 and condenser 12 etc. is formed, filler 19 and feed valve 4 is established above evaporating kettle 1, water suction tower 8 is arranged at above evaporating kettle 1, bottom is stored still 7 respectively by pipeline with evaporating kettle 1 and phosphoric acid and is connected, filler 9 is established in inside, shower nozzle 10 is established at top, top arranges dehydrating kettle 19, bottom dehydrating kettle 19, leakage fluid dram is set, be connected with shower nozzle 10 by the pipeline of band phosphoric acid valve 11, water suction tower 8 side sets out steam ports near tower top place, be connected by the steam inlet of pipeline with the prolong 13 in condenser 12, the exit end of prolong 13 is communicated with formic acid storagetank 16 by the pipeline of carries product valve 15, storage still 7 bottom discharge port arranges Phosphoric Acid Circulating Pump 20, bottom in its inlet pipe access phosphoric acid storage still 7, outlet pipe inserts in dehydrating kettle 19, dehydrating kettle 19 upper side wall arranges Crude product input valve 17, lower wall arranges heating medium inlet valve 18.Technical process concrete steps are: (1) adopts thermal dehydration still, removes the moisture content in dilute phosphoric acid, obtains thick polyphosphoric acid and high-concentration phosphoric acid; (2) allow thick polyphosphoric acid and high-concentration phosphoric acid dirty along packing layer in water suction tower, after absorbing moisture content, become dilute phosphoric acid gradually, then flow to dilute phosphoric acid storage still; (3) with pump, dilute phosphoric acid is sent into dehydrating kettle, realize phosphoric acid circulation and utilize.(4) adopt evaporating kettle evaporation formic acid solution, obtain the dilute formic acid steam that mass concentration is 20 ~ 80%; (5) formic acid vapor is allowed first by cold filling layer above evaporating kettle or the packing layer that has charging dilute formic acid solution dirty, solid entrainment in removing formic acid vapor; (6) by there being the water suction tower of thick polyphosphoric acid and the dirty packing layer of high-concentration phosphoric acid, the most of moisture content in removing formic acid vapor; (7) formic acid vapor after concentrating becomes concentration formic acid and high liquid by condensing tube condensation.When implementing of the present invention, first add dilute phosphoric acid to dehydrating kettle 19, open Crude product input valve 17 and heating medium inlet valve 18, heat the moisture removed in dilute phosphoric acid; When still liquid temp to be drained off is raised to 150-350 DEG C, dilute phosphoric acid becomes polyphosphoric acid and high-concentration phosphoric acid; Then open phosphoric acid valve 11, allow thick polyphosphoric acid and high-concentration phosphoric acid flow into packing layer, while flow downward, limit absorbs moisture content, finally flows to phosphoric acid storage still 7.Then add appropriate dilute formic acid to evaporating kettle 1, then open heating steam valve 5 and water coolant water intaking valve 14 successively.After a while, the dilute formic acid liquid boiling in evaporating kettle 1, the steam of generation rises to packing layer 21, and removing solid entrainment, then enters bottom water suction tower 8 from connecting tube 6.In the process of steam flowing in water suction tower 8, the polyphosphoric acid on filled 9 surfaces of moisture content and highly concentrated phosphoric acid absorb.The steam rising to water suction tower 8 top enters prolong 13 in condenser 12, is condensed into dense formic acid, flows to formic acid storagetank 16.When evaporating kettle 1 liquid level is lower than discharge port, open bleeder valve 3 and feed valve 4, and zinecarboxylic acid feed rate and heating medium inlet flow rate are adjusted to certain value.When storing the rare METHAPHOSPHORIC ACID liquid level in still 7 and reaching 1/2 to 2/3, automatically start recycle pump 20, dilute phosphoric acid is sent into dehydrating kettle 19.
Claims (2)
1. a recovery method for trade effluent dilute formic acid, is characterized in that: adopt phosphoric acid circulation to carry out concentration and recovery to dilute formic acid, concrete technology flow process is:
(1) adopt thermal dehydration still, remove the moisture content in dilute phosphoric acid, obtain thick polyphosphoric acid and high-concentration phosphoric acid;
(2) allow thick polyphosphoric acid and high-concentration phosphoric acid dirty along packing layer in water suction tower, after absorbing moisture content, become dilute phosphoric acid gradually, then flow to dilute phosphoric acid storage still;
(3) with pump, the dilute phosphoric acid in storage still is sent into dehydrating kettle, realize phosphoric acid circulation and utilize;
(4) adopt evaporating kettle evaporation formic acid solution, obtain the dilute formic acid steam that mass concentration is 20 ~ 80%;
(5) formic acid vapor is allowed first by cold filling layer above evaporating kettle or the packing layer that has charging dilute formic acid solution dirty, solid entrainment in removing formic acid vapor;
(6) by there being the water suction tower of thick polyphosphoric acid and the dirty packing layer of high-concentration phosphoric acid, the most of moisture content in removing formic acid vapor;
(7) formic acid vapor after concentrating becomes in concentration formic acid and high liquid inflow storage tanks to store by condensing tube condensation.
2. the retrieving arrangement of a trade effluent dilute formic acid, it comprises evaporating kettle (1), water suction tower (8), storage still (7) and condenser (12), it is characterized in that: filler (21) and feed valve (4) are established in evaporating kettle (1) top, water suction tower (8) is arranged at evaporating kettle (1) top, bottom is stored still (7) respectively by pipeline and evaporating kettle (1) and phosphoric acid and is connected, filler (9) is established in inside, shower nozzle (10) is established at top, top arranges dehydrating kettle (19), dehydrating kettle (19) bottom arranges leakage fluid dram, be connected with shower nozzle (10) by the pipeline of band phosphoric acid valve (11), water suction tower (8) side sets out steam ports near tower top place, be connected by the steam inlet of pipeline with the prolong (13) in condenser (12), the exit end of prolong (13) is communicated with formic acid storagetank (16) by the pipeline of carries product valve (15), storage still (7) bottom discharge port arranges Phosphoric Acid Circulating Pump (20), its inlet pipe access phosphoric acid storage still (7) interior bottom, outlet pipe inserts in dehydrating kettle (19), dehydrating kettle (19) upper side wall arranges Crude product input valve (17), lower wall arranges heating medium inlet valve (18).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310362587.6A CN104418723B (en) | 2013-08-20 | 2013-08-20 | The recovery method of trade effluent dilute formic acid and device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310362587.6A CN104418723B (en) | 2013-08-20 | 2013-08-20 | The recovery method of trade effluent dilute formic acid and device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104418723A CN104418723A (en) | 2015-03-18 |
| CN104418723B true CN104418723B (en) | 2016-01-20 |
Family
ID=52968934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310362587.6A Expired - Fee Related CN104418723B (en) | 2013-08-20 | 2013-08-20 | The recovery method of trade effluent dilute formic acid and device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104418723B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105435596B (en) * | 2015-11-13 | 2019-06-11 | 昆明理工大学 | The new application of polyphosphoric acids |
| CN111204827B (en) * | 2020-01-17 | 2022-04-15 | 陕西能源职业技术学院 | Chemical wastewater purification device |
| CN115353450A (en) * | 2022-09-26 | 2022-11-18 | 河北康壮环保科技股份有限公司 | Process for concentrating dilute formic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1133833A (en) * | 1994-04-07 | 1996-10-23 | 戈里特斯奇公司 | Method and apparatus for recovering carboxylic acids from aqueous solutions |
| CN101391945A (en) * | 2008-10-27 | 2009-03-25 | 浙江工业大学 | Novel purification method for formic acid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS585895B2 (en) * | 1980-07-17 | 1983-02-02 | 日本ソレツクス株式会社 | Separation method of organic acids |
-
2013
- 2013-08-20 CN CN201310362587.6A patent/CN104418723B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1133833A (en) * | 1994-04-07 | 1996-10-23 | 戈里特斯奇公司 | Method and apparatus for recovering carboxylic acids from aqueous solutions |
| CN101391945A (en) * | 2008-10-27 | 2009-03-25 | 浙江工业大学 | Novel purification method for formic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104418723A (en) | 2015-03-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103012104B (en) | Method for treating butanol-octanol waste alkali liquor and recycling butyric acid | |
| CN101549929B (en) | Method for distilling absorption type negative-pressure thermal cycle coking wastewater | |
| CN106866368A (en) | Alcoholic gas field sewage methanol recovery device and technique based on air- extraction and vacuum membrane distillation method | |
| CN104418723B (en) | The recovery method of trade effluent dilute formic acid and device | |
| CN203683302U (en) | Evaporating device for wastewater with high content of salt | |
| CN104085861B (en) | A kind of device of reclaim(ed) sulfuric acid from Graphene acid-bearing wastewater and corresponding technique thereof | |
| CN204174031U (en) | The treatment unit of refuse leachate reverse osmosis dope | |
| CN104030379B (en) | A kind of vaporizer processing oily(waste)water | |
| CN103408082B (en) | Recovery method and device for formic acid solvent during metronidazole production | |
| CN205759788U (en) | Energy-saving single-action concentrates rectifier unit | |
| CN107501126B (en) | The method and system of high efficiente callback acrylonitrile in a kind of production of high-performance carbon fibre | |
| CN103833094B (en) | A kind for the treatment of process of high-salt wastewater | |
| CN204417424U (en) | Super-viscous oil SAGD cyclic preheat liquid treating system | |
| CN104774143A (en) | Cycle recovery method of formic acid solvent in metronidazole production process | |
| CN205710514U (en) | A kind of purifying ethylene glycol piece-rate system | |
| CN203429086U (en) | Device for circularly concentrating dilute formic acid through phosphoric acid | |
| CN203440262U (en) | Device for producing trans-1, 2-dichloroethylene with acetylene by adopting catalytic chlorination method | |
| CN207451656U (en) | A kind of continuous removal of ammonia and nitrogen light component organic matter and salt system | |
| CN203715538U (en) | Rectifying and purifying device for ethyl acetate under vacuum state | |
| CN204502443U (en) | For the liquid-ring vacuum pump system of Benzene Chloride rectification under vacuum | |
| CN206288970U (en) | A kind of thio conversion ammonium sulfate process equipment of desulphurization waste liquid of coke oven gas salt extraction | |
| CN210065601U (en) | Ultra-clean high-purity absolute ethyl alcohol production line | |
| CN105273750A (en) | Supper heavy oil SAGD circulation preheating liquid processing system | |
| CN204224268U (en) | A kind of sodium-chlor crystallization retrieving arrangement accelerating evaporation concentration speed | |
| CN220695849U (en) | Novel device for purifying amine liquid by thermal method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160120 Termination date: 20210820 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |