CN103803691A - Low-concentration formic acid wastewater treatment process - Google Patents
Low-concentration formic acid wastewater treatment process Download PDFInfo
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- CN103803691A CN103803691A CN201410102355.1A CN201410102355A CN103803691A CN 103803691 A CN103803691 A CN 103803691A CN 201410102355 A CN201410102355 A CN 201410102355A CN 103803691 A CN103803691 A CN 103803691A
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- formic acid
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 245
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 121
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000008569 process Effects 0.000 title claims abstract description 28
- 238000004065 wastewater treatment Methods 0.000 title abstract description 3
- 239000002351 wastewater Substances 0.000 claims abstract description 80
- 238000000605 extraction Methods 0.000 claims abstract description 72
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000005886 esterification reaction Methods 0.000 claims abstract description 27
- 150000002148 esters Chemical class 0.000 claims abstract description 23
- 238000012856 packing Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000007921 spray Substances 0.000 claims description 32
- 150000001298 alcohols Chemical class 0.000 claims description 21
- 230000032050 esterification Effects 0.000 claims description 20
- 230000004907 flux Effects 0.000 claims description 20
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 15
- 230000009471 action Effects 0.000 claims description 12
- 230000005484 gravity Effects 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 7
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- 238000000889 atomisation Methods 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- 238000003809 water extraction Methods 0.000 claims description 3
- 239000013589 supplement Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract 2
- 239000012044 organic layer Substances 0.000 abstract 2
- 238000005507 spraying Methods 0.000 abstract 1
- 230000004044 response Effects 0.000 description 8
- 238000004821 distillation Methods 0.000 description 5
- -1 alcohol ester Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000005446 dissolved organic matter Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000004460 silage Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
The invention provides a low-concentration formic acid wastewater treatment process, wherein the low-concentration formic acid wastewater having the mass fraction of 0.1%-3% is atomized and sprayed into an esterification-extraction tower, the spraying density is 8-50m<3>/(m<2>.h), the atomized water drops are evenly distributed in packing at the upper part in the tower and finally naturally settles in a higher-alcohol oil phase; in the settling process, the water drops are in contact with the alcohol for not less than 120s, and then the formic acid in the water is heated to have an esterification reaction with the alcohol, and after the formic acid is transformed into a corresponding formic ester, the formic ester is extracted in the oil phase, wherein the reaction temperature ranges from 85 DEG C to 105 DEG C and is maintained by introduced water vapor. The water removed from the formic acid continuously falls to a water layer at the bottom of the tower, the heat of the water is used for preheating the initial formic acid wastewater, and the water layer is subjected to simple biochemical treatment after being extracted. The organic layer at the lower part of the esterification-extraction tower is extracted to a rectifying tower for vacuum rectification so that the ester and the alcohol in the organic layer are separated from each other; high-purity ester is extracted from the top of the tower, and high-temperature alcohol at the bottom of the tower is supplemented with a part of alcohol and then fed into the esterification-extraction tower to be recycled.
Description
Technical field
The present invention relates to a kind for the treatment of process of lower concentration formic acid wastewater.
Background technology
Formic acid (CH
2o
2) be called again formic acid, colourless and have pungent odour, and be corrosive, 100.8 ℃ of boiling points.Because the structure of formic acid is special, its hydrogen atom is directly connected with carboxyl, also can regard a hydroxyl formaldehyde as, and therefore formic acid has the character of acid and aldehyde simultaneously.In chemical industry, formic acid is widely used in the productions such as fabrics printing and dyeing, leather processing, Rubber processing, silage and medicine.
The boiling point of formic acid is 100.8 ℃, almost with water with and dissolve each other with water, Interpolymer Association is extremely strong, if formic acid dilute solution is used merely distillation method concentrate, poor effect.And in the time that temperature is higher, formic acid is volatile.
Table 1: the relation between Analysis of Formic acid Residual and formic acid wastewater temperature
| Temperature/℃ | 70 | 65 | 60 | 55 | 50 | 45 | 40 | 35 | 30 | 20 |
| Analysis of Formic acid Residual/% | 3.9 | 5.1 | 5.9 | 6.8 | 8.2 | 9.0 | 9.2 | 9.2 | 9.2 | 9.6 |
As shown in table 1, below 40 ℃ time, the formic acid concn in water is basicly stable in 9.2% left and right, but in the time that temperature raises, formic acid concn can sharply decline, and during to 70 ℃, only has 4% left and right.At present esterification process is processed formic acid wastewater, and temperature is generally more than 85 ℃, so formic acid concn is convenient to process when above 3% in trade effluent, and formic acid concn is when higher, and general usual way is more difficult or processing cost is larger.
At present, for adopting the treatment processs of formic acid decomposition containing the research of formic acid treatment of Organic Wastewater, as oxidation style, catalytic decomposition, biochemical treatment process, absorption method and electrolytic process etc., although these method treatment effects are relatively good, but often cost is higher, treatment capacity is very little, is not suitable for industrial applications.Industrial more use rectification method or esterification distillation method or azeotropic-fractionation combine recovery, process formic acid wastewater.Wherein rectification method, because the boiling point of formic acid and water is very approaching, therefore can not use separately.The ultimate principle of esterification process is to make formic acid and alcohols generation esterification, and reaction equation is as follows:
HCOOH+ROH→HCOOR+H
2O
These class methods adopt esterification, rectifying two steps to complete the processing to formic acid wastewater conventionally, can the higher formic acid wastewater of concentration for the treatment of.For the formic acid wastewater of lower concentration (<4%), water proportion is very high, and while adding thermal wastewater and rectifying, required energy consumption is larger, and the cost of processing waste water is very high, and formic acid wastewater has corrodibility, can strengthening corrosion sewage treatment equipment under high temperature.
Summary of the invention
The object of this invention is to provide a kind of novel process of lower concentration formic acid wastewater processing of less energy-consumption, first in esterification-extraction tower, make formic acid and higher alcohols generation esterification in waste water become ester class, dissolution extraction is in higher alcohols, thereby separate with water, discharge of wastewater after layering, the further rectifying separation ester of oil phase and alcohol, alcohol is reused for esterification-extraction process.
For realizing above-mentioned target, technical scheme of the present invention is as follows:
A kind for the treatment of process of lower concentration formic acid wastewater.Its flow process as shown in Figure 1, comprises the following steps:
(1) be that 0.1%～3% lower concentration formic acid wastewater sprays to esterification-extraction tower 2 through atomizer spray equipment 5 after by formic acid wastewater preheating pipe 1 and 15 preheatings of formic acid wastewater interchanger by containing massfraction, the epimere of esterification-extraction tower arranges packing layer 3, middle part passes into raw steam heating alcohol by steam-heated pipe line 13, enhance esterification speed, after heating, alcohol temperature remains on 85～110 ℃, and the spray flux of atomizer spray equipment 5 is 10～50m
3/ (m
2h), droplet moves downward and is uniformly distributed in packing layer 3 inside of esterification-extraction tower 2 under action of gravity, spray flux is different according to device treatment scale and higher alcohols recoverable amount, higher alcohols are selected water-fast alcohol, comprise propyl carbinol, Pentyl alcohol or primary isoamyl alcohol etc., the add-on of higher alcohols is determined according to tower diameter size, generally account for tower body long-pending 1/2～2/3 between, generally need complete submergence packing layer (3), formic acid wastewater droplet is dispersed in filler, slowly enter after higher alcohols liquid internal, sedimentation downwards under action of gravity, water droplet moves to oil reservoir bottom from entering top of oil horizon, be not less than 120s duration of contact with higher alcohols, in this process, water droplet is heated rapidly by alcohol, formic acid in water droplet fully contacts and occurs to enter oil phase after esterification with alcohol around, because formic acid wastewater spray flux is much smaller than the alcohol amount in tower, so can be heated rapidly in tower, simultaneously, because the amount of alcohol is much larger than amount of formic acid, promote positive reaction balance to move, accelerated esterification reaction rate,
The object of the formic acid wastewater preheating described in technique of the present invention is not only in order to promote formic acid wastewater inlet temperature of stabilizer, main object is formic acid wastewater temperature after reduction esterification-extraction tower bottom treatment, make wherein dissolved organic matter get back to oil reservoir, reduce and purify organic content in rear formic acid wastewater, formic acid wastewater atomizing spray object is also not only for formic acid is fully contacted with tower medium high carbon alcohol, heated rapidly, reach the required temperature of esterification; For formic acid in waste water fully contacts with alcohols, part formic acid can be dissolved in alcohol especially, reach the object of extraction.
(2) formic acid wastewater after treatment is from 2 bottom water layer 12 extraction of esterification-extraction tower, produced quantity approximates atomisation unit spray flux, the formic acid wastewater of bottom extraction wherein formic acid content, lower than 0.05%, can directly be discharged or be discharged after simple biochemical treatment by waste water extraction pipeline 14;
Processed waste water described in technique of the present invention is the heat in order to make full use of extraction formic acid wastewater for the object of the preheating of initial formic acid wastewater, improve the temperature that the initial formic acid wastewater of formic acid enters esterification-extraction tower, make it reach rapidly the required temperature of esterification, thereby reduce the energy consumption of a whole set for the treatment of system.
(3) esterification-extraction tower 2 mesonexine oil 4 pass through pump 6 extraction to separation column 7, in oily mater, mainly contain higher alcohols, ester class and minute quantity formic acid, in tower 7 by the rectifying of oil reservoir liquid pressure-reducing, ester can be separated with alcohol, after rectifying, ester class is through piping 8 extraction, alcohol at the bottom of tower is delivered to esterification-extraction tower 2 by pipeline 9 and is recycled, and continues on for esterification extraction process, and the alcohol of middle loss supplements by mending alcohol pipeline 10.
In technique of the present invention, be the Ester of formic acid esterification gained through the material of extraction pipeline 8 extraction, at the bottom of tower higher alcohols can continue on for esterification in esterification-extraction tower 2, object is in order to make its recycle, cost-saving, increases economic efficiency.
Accompanying drawing explanation
Fig. 1 is the process schematic representation of lower concentration formic acid wastewater of the present invention processing, wherein: 1-formic acid wastewater preheating pipe; 2-esterification-extraction tower; 3-packing layer; 4-oil reservoir; 5-spray equipment; 6-oil reservoir extraction pump; 7-separation column; 8-ester class extraction pipeline; 9-alcohol circulating line; 10-mends alcohol pipeline; 11-formic acid wastewater transport pipe; 12-water layer; 13-steam-heated pipe line; Waste water extraction pipeline after 14-purifies; 15-formic acid wastewater interchanger.
Embodiment
Below by embodiment, the present invention is specifically described, but can not be interpreted as the restriction to scope of patent protection of the present invention.
Embodiment 1:
(1) the lower concentration formic acid wastewater that contains 1% is sprayed to esterification-extraction tower 2 by atomizing sprayer 5, tower diameter 0.8m, tower height 6m, spray flux is 50m
3/ (m
2h), it is moved downward under action of gravity and be uniformly distributed in packing layer 3 inside, in esterification-extraction tower 2, hypomere is propyl carbinol, and volume is 1.8m
3, pipeline 13 passes into steam heating propyl carbinol, and n-butanol layer temperature is 85 ℃.Formic acid wastewater droplet is dispersed in filler, slowly enter lower floor's propyl carbinol liquid internal, sedimentation downwards under action of gravity, profit two-phase is about 150s abundant duration of contact, in this process, because formic acid wastewater spray flux is very little with respect to the recoverable amount of tower bottom propyl carbinol, water droplet is heated rapidly; The recoverable amount of propyl carbinol is greatly excessive with respect to amount of formic acid, promotes positive reaction balance to move, and accelerates esterification reaction rate.
(2) stable rear esterification-extraction tower tower 2 bottom water layer 12 formic acid wastewater after treatment of question response is by formic acid wastewater in interchanger 15 preheating pipes 1, after heat exchange, water temperature declines 12 ℃, and wherein formic acid content is 0.04%, then from pipeline 14 extraction, be delivered to biochemistry pool processing.After processing, formic acid wastewater produced quantity equals atomisation unit spray flux, is about 6m
3/ h, in pipeline 1, after formic acid wastewater preheating, water temperature is 52 ℃, is then delivered to tower top spray by pipeline 11.
(3) when question response is stablized, esterification-extraction tower 2 mesonexine oil 4 are passed through to pump 6 extraction to separation column 7, in oily mater, mainly contain butanols, ester class and minute quantity formic acid, in separation column 7, oil reservoir liquid pressure-reducing is distilled, alcohol ester can be separated with formic acid, after distillation, ester class is through piping 8 extraction, propyl carbinol at the bottom of tower is delivered to esterification-extraction tower 2 by pipeline 9 and is recycled, and continues on for esterification extraction process.
Embodiment 2:
(1) formic acid wastewater containing 0.1% is sprayed to esterification-extraction tower 2 by atomizing sprayer 5, tower diameter 0.9m, tower height 8m, spray flux is 15m
3/ (m
2h), it is moved downward under action of gravity and be uniformly distributed in packing layer 3 inside of esterification-extraction tower 2, in tower 2, hypomere is primary isoamyl alcohol, and recoverable amount is 3.2m
3, pipeline 13 passes into steam heating primary isoamyl alcohol, and primary isoamyl alcohol phase temperature is 105 ℃.Formic acid wastewater droplet is dispersed in filler, slowly enter lower floor's higher alcohols liquid internal, sedimentation downwards under action of gravity, profit two-phase is about 135s abundant duration of contact, in this process, because formic acid wastewater spray flux is very little with respect to the recoverable amount of tower bottom alcohol, water droplet is heated rapidly; The recoverable amount of alcohol is greatly excessive with respect to amount of formic acid, promotes positive reaction balance to move, and accelerates esterification reaction rate.
(2) stable rear esterification-extraction tower 2 bottom water layer 12 formic acid wastewater after treatment of question response is by formic acid wastewater in interchanger 15 preheating pipes 1, after heat exchange, formic acid wastewater temperature after treatment declines 8 ℃, wherein formic acid content is 0.01%, then from pipeline 14 extraction, discharge after being delivered to biochemistry pool simple process.After processing, formic acid wastewater produced quantity equals atomisation unit spray flux, is about 6m
3/ h, in pipeline 1, after formic acid wastewater preheating, water temperature is 46 ℃, is then delivered to tower top spray by pipeline 11.
(3) when question response is stablized, esterification-extraction tower 2 mesonexine oil 4 are passed through to pump 6 extraction to separation column 7, in oily mater, mainly contain primary isoamyl alcohol, ester class and minute quantity formic acid, in separation column 7 by the rectifying of oil reservoir liquid pressure-reducing, ester can be separated with alcohol, after rectifying, ester class is through piping 8 extraction, separation column 7 bottom primary isoamyl alcohol are delivered to esterification-extraction tower 2 by pipeline 9 and are recycled, and continue on for esterification extraction process.
Embodiment 3:
(1) the lower concentration formic acid wastewater that contains 2% is sprayed to esterification-extraction tower 2 by atomizing sprayer 5, tower diameter 1.0m, tower height 7m, spray flux is 12m
3/ (m
2h), it is moved downward under action of gravity and be uniformly distributed in packing layer 3 inside, in esterification-extraction tower 2, hypomere is Pentyl alcohol, and recoverable amount is 6m
3, pipeline 13 passes into steam heating Pentyl alcohol, keeps 105 ℃ mutually of Pentyl alcohols.Formic acid wastewater droplet is dispersed in filler, slowly enter lower floor's higher alcohols liquid internal, sedimentation downwards under action of gravity, profit two-phase is about 140s abundant duration of contact, in this process, because formic acid wastewater spray flux is very little with respect to the recoverable amount of tower bottom alcohol, water droplet is heated rapidly; The recoverable amount of alcohol is greatly excessive with respect to amount of formic acid, promotes positive reaction balance to move, and accelerates esterification reaction rate.
(2) stable rear tower 2 bottom water layer 12 formic acid wastewater after treatment of question response is by formic acid wastewater in interchanger 15 preheating pipes 1, after heat exchange, formic acid wastewater temperature after treatment declines 8 ℃, and wherein formic acid content is 0.04%, then from pipeline 14 extraction, discharge after being delivered to biochemistry pool simple process.After processing, formic acid wastewater produced quantity equals atomisation unit spray flux, is about 9.5m
3/ h, in pipeline 1, after formic acid wastewater preheating, water temperature is 45 ℃, is then delivered to tower top spray by pipeline 11.
(3) when question response is stablized, esterification-extraction tower 2 mesonexine oil 4 are passed through to pump 6 extraction to separation column 7, in oily mater, mainly contain Pentyl alcohol, ester class and minute quantity formic acid, in separation column 7, oil reservoir liquid pressure-reducing is distilled, alcohol ester can be separated with formic acid, after distillation, ester class is through piping 8 extraction, Fractionator Bottom Pentyl alcohol is delivered to esterification-extraction tower 2 by pipeline 9 and is recycled, and continues on for esterification extraction process.
Embodiment 4:
(1) the lower concentration formic acid wastewater that contains 3% is sprayed to esterification-extraction tower 2 by atomizing sprayer 5, tower diameter 0.85m, tower height 6.5m, spray flux is 12m
3/ (m
2h), it is moved downward under action of gravity and be uniformly distributed in packing layer 3 inside, in esterification-extraction tower tower 2, hypomere is propyl carbinol, and recoverable amount is 2.6m
3, pipeline 13 passes into steam heating propyl carbinol, and propyl carbinol phase temperature is 85 ℃.Formic acid wastewater droplet is dispersed in filler, slowly enter lower floor's higher alcohols liquid internal, sedimentation downwards under action of gravity, profit two-phase is about 140s abundant duration of contact, in this process, because formic acid wastewater spray flux is very little with respect to the recoverable amount of tower bottom alcohol, water droplet is heated rapidly; The recoverable amount of alcohol is greatly excessive with respect to amount of formic acid, promotes positive reaction balance to move, and accelerates esterification reaction rate.
(2) stable rear tower 2 bottom water layer 12 formic acid wastewater after treatment of question response is by formic acid wastewater in interchanger 15 preheating pipes 1, after heat exchange, formic acid wastewater temperature after treatment declines 8 ℃, and wherein formic acid content is 0.05%, then from pipeline 14 extraction, discharge after being delivered to biochemistry pool simple process.After processing, formic acid wastewater produced quantity equals atomisation unit spray flux, is about 6.7m
3/ h, in pipeline 1, after formic acid wastewater preheating, water temperature is 48 ℃, is then delivered to tower top spray by pipeline 11.
(3) when question response is stablized, esterification-extraction tower 2 mesonexine oil 4 are passed through to pump 6 extraction to separation column 7, in oily mater, mainly contain propyl carbinol, ester class and minute quantity formic acid, in separation column 7, oil reservoir liquid pressure-reducing is distilled, alcohol, ester can be separated with formic acid, after distillation, ester class is through piping 8 extraction, Fractionator Bottom alcohol is delivered to esterification-extraction tower 2 by pipeline 9 and is recycled, and continues on for esterification extraction process.
Claims (2)
1. a treatment process for lower concentration formic acid wastewater, comprises the following steps:
(1) be that 0.1%～3% lower concentration formic acid wastewater sprays to esterification-extraction tower (2) through atomizer spray equipment (5) after by preheating pipe (1) and formic acid wastewater interchanger (15) preheating by containing massfraction, the epimere of esterification-extraction tower arranges packing layer (3), middle part passes into raw steam heating alcohol by steam-heated pipe line (13), enhance esterification speed, after heating, alcohol temperature remains on 85～110 ℃, and the spray flux of atomizer spray equipment (5) is 10～50m
3/ (m
2h), droplet moves downward and is uniformly distributed in packing layer (3) inside of esterification-extraction tower (2) under action of gravity, spray flux is different according to device treatment scale and higher alcohols recoverable amount, higher alcohols are selected water-fast alcohol, the add-on of higher alcohols is determined according to tower diameter size, should account for tower body long-pending 1/2～2/3 between, need complete submergence packing layer (3), formic acid wastewater droplet is dispersed in filler, slowly enter after higher alcohols liquid internal, sedimentation downwards under action of gravity, water droplet moves to oil reservoir bottom from entering top of oil horizon, be not less than 120s duration of contact with higher alcohols, in this process, water droplet is heated rapidly by alcohol, formic acid in water droplet fully contacts and occurs to enter oil phase after esterification with alcohol around, because formic acid wastewater spray flux is much smaller than the alcohol amount in tower, so can be heated rapidly in tower, simultaneously, because the amount of alcohol is much larger than amount of formic acid, promote positive reaction balance to move, accelerated esterification reaction rate,
(2) formic acid wastewater after treatment is from water layer (12) extraction of esterification-extraction tower (2) bottom, produced quantity equals atomisation unit spray flux, the formic acid wastewater of bottom extraction wherein formic acid content, lower than 0.05%, is directly discharged or is discharged after simple biochemical treatment by waste water extraction pipeline (14);
(3) esterification-extraction tower (2) mesonexine oil (4) passes through pump (6) extraction to separation column (7), in oily mater, mainly contain higher alcohols, ester class and minute quantity formic acid, in separation column (7) by the rectifying of oil reservoir liquid pressure-reducing, ester is separated with alcohol, after rectifying, ester class is through piping (8) extraction, alcohol at the bottom of separation column tower is delivered to esterification-extraction tower (2) by pipeline (9) and is recycled, continue on for esterification extraction process, in the middle of process, the alcohol of loss supplements by mending alcohol pipeline (10).
2. the treatment process of lower concentration formic acid wastewater according to claim 1, is characterized in that: described higher alcohols comprise propyl carbinol, Pentyl alcohol or primary isoamyl alcohol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113072445A (en) * | 2021-04-02 | 2021-07-06 | 淄博腾煜化工工程有限公司 | Method for preparing formate by using byproduct formic acid of nitromethane method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3983010A (en) * | 1974-02-15 | 1976-09-28 | Basf Aktiengesellschaft | Recovery of the formic acid/water azeotrope by distillation |
| CN1354139A (en) * | 2000-11-16 | 2002-06-19 | 亚新技术株式会社 | Method and device for treating waste water containing acetic acid |
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2014
- 2014-03-19 CN CN201410102355.1A patent/CN103803691B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3983010A (en) * | 1974-02-15 | 1976-09-28 | Basf Aktiengesellschaft | Recovery of the formic acid/water azeotrope by distillation |
| CN1354139A (en) * | 2000-11-16 | 2002-06-19 | 亚新技术株式会社 | Method and device for treating waste water containing acetic acid |
Non-Patent Citations (1)
| Title |
|---|
| 张晓娟 等: "从环己醇和环己酮甲酸废水中回收甲酸酯", 《沈阳工业大学学报》, vol. 30, no. 6, 31 December 2008 (2008-12-31) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113072445A (en) * | 2021-04-02 | 2021-07-06 | 淄博腾煜化工工程有限公司 | Method for preparing formate by using byproduct formic acid of nitromethane method |
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