CN110092711A - A kind of formaldehyde separation method of butanol purifying technique - Google Patents
A kind of formaldehyde separation method of butanol purifying technique Download PDFInfo
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- CN110092711A CN110092711A CN201910417826.0A CN201910417826A CN110092711A CN 110092711 A CN110092711 A CN 110092711A CN 201910417826 A CN201910417826 A CN 201910417826A CN 110092711 A CN110092711 A CN 110092711A
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- butanol
- formaldehyde
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
Abstract
A kind of formaldehyde separation method of butanol purifying technique, raw material butanol solution is after feed preheater preheats, rectifying separation is carried out into butanol lightness-removing column, to tower top, kettle material is pumped through tower reactor pressurizes, send after feed preheater and cooler are cooling to chromatography device multi_layer extraction the distillation of the mixture of main light component methanol, propyl alcohol and a small amount of butanol and water；Butanol water process column overhead is that butanol-water azeotrope gas phase is sent into lightness-removing column, and tower reactor is enriched the aqueous solution of formaldehyde, is directly sent with hot water conditions to the reaction tank of water containing aldehyde；Removal formaldehyde components are separated by oxidation reaction.The present invention handles to 30mg/L or less the formaldehyde components of the 50-15000 mg/L in acetylene-formaldehyde process BDO process by-product butanol, drastically reduce total wastewater discharge, formaldehyde pollutants are transformed into other innocuous substances by the method for the invention and are eliminated pollution factor, the promotion for realizing working environment improves the occupational health condition of operating staff.
Description
Technical field
The invention belongs to chemical technology fields, more particularly to a kind of formaldehyde separation method of butanol purifying technique.
Background technique
1,4-butanediol abbreviation BDO is a kind of important basic organic chemical industry and fine chemical material.Using acetylene-formaldehyde process
During technique produces 1,4-butanediol, ethynylation device is compound in acetylene copper and acetylene bismuth using formaldehyde and acetylene as raw material
It reacts under catalyst action, firstly generates Isosorbide-5-Nitrae-butynediols (BYD), then BYD is under the conditions of certain pressure, in thunder Buddhist nun
Under Raney nickel effect, it is hydrogenated to 1,4-butanediol (BDO), using being refining to obtain 1,4-butanediol product.The production
The butanol of Cheng Zhonghui by-product considerable amount.Meanwhile the residual raw materials formaldehyde not reacted completely can also enter by-product butanol solution
In.
During purifying to by-product butanol solution, residual formaldehyde therein must try every possible means to be removed, no
It then just will affect the quality of butanol byproduct, and enter downstream wastewater Treatment stations with waste water to influence its normal operation.For
Using the sewage farm of biological degradation method, this substance of formaldehyde has the microorganism in the activated sludge of sewage farm very strong
Toxicity.Content of formaldehyde is exceeded in sewage, so that the activated sludge of downstream wastewater processing system is poisoned, at sewage
It manages system disorders and has serious consequences.General requirement of the sewage farm to content of formaldehyde in received aldehyde-containing sewage should be less than
30 mg/L, when concentration of formaldehyde reaches 150 mg/L, microbial activity can be reduced to original active half, when concentration is more than 200
When mg/L, microbial activity can be suppressed completely, will seriously affect wastewater treatment efficiency.
Currently, there are no good methods to be pocessed for material containing aldehyde, general way is will to need to arrange with a large amount of clear water
The material containing aldehyde put is diluted to and is pocessed less than being emitted into sewage farm after 30 mg/L successively.
Summary of the invention
The present invention for it is existing by-product butanol solution is purified during, residual formaldehyde does not separate removal
Problem proposes a kind of formaldehyde separation method of butanol purifying technique.
The butanol solution of acetylene-formaldehyde process BDO process by-product, to purify butanol product, wherein containing 50-15000 mg/L's
Formaldehyde components.Formaldehyde has an impact to butanol product quality and waste discharge, and PARA FORMALDEHYDE PRILLS(91,95) component of the present invention is steamed by using physics
It evaporates and chemically reacts two kinds of methods and separated abjection.
Realize the technical solution of the object of the invention are as follows: raw material butanol solution is de- into butanol after feed preheater preheats
The mixture of light tower progress rectifying separation, main light component methanol, propyl alcohol and a small amount of butanol and water is distilled to tower top, tower reactor
Material is sent through the pressurization of tower reactor pump, after feed preheater and cooler are cooling to chromatography device multi_layer extraction；Chromatograph device upper layer butanol
Phase solution is directly entered butanol product tower and carries out rectifying, obtains butanol product；Chromatography device lower water mixes in liquid enrichment raw material
The formaldehyde components brought into recycle butanol therein into butanol water process tower rectifying；Butanol water process column overhead is that butanol-water is total
Object is boiled, gas phase is sent into butanol lightness-removing column, and tower reactor is enriched the aqueous solution of formaldehyde, directly send with hot water conditions to water containing aldehyde and reacts
Pond；When reaching setting value wait react pit level, water containing aldehyde switches to another reaction tank, and carbide slag object is at this moment added into reaction tank
Material, starting stirring, allows carbide slag to be completely dissolved in hot water, meanwhile, appropriate steam (LS), which is supplemented, to reaction tank maintains pond temperature
Degree blasts compressed air (OA) to reaction tank at 80-90 DEG C, and in time.
There are two identical series in parallel for the reaction cell system, when one of series is in reactiveness, separately
One series of reception water containing aldehyde, then switching uses guarantee continuous production.
A variety of reaction hairs such as oxidation reaction, neutralization reaction, Formose Reaction, aldol condensation, acyloin condensation are shared in reaction tank 8
It is raw, removal formaldehyde components are separated by chemical reaction, reaction equation is as follows:
Oxidation reaction is to oxidize the formaldehyde into formic acid by the oxygen in the compressed air (OA) that is passed through to reaction tank 8, and formic acid is again
Neutralization reaction occurs for the calcium hydroxide for being dissolved in water generation with the carbide slag of addition, generates calcium formate and reaches separation abjection formaldehyde
Purpose.In Formose Reaction, aldol condensation, three kinds of acyloin condensation reactions, although the calcium hydroxide that carbide slag generates is not participated in instead
It answers, but plays the role of catalyst, formaldehyde is transformed into polymer to achieve the purpose that separation abjection.
The present invention has following remarkable result:
(1) present invention purifies to Product-level to acetylene-formaldehyde process BDO process by-product butanol, and by the first of 50-15000 mg/L therein
Aldehyde component is handled to 30mg/L or less;
(2) present invention, which solves in traditional handicraft, dilutes high aldehyde-containing sewage with a large amount of clear water, is then discharged into sewage farm again,
The problem of causing wastewater flow rate to increase in several times, drastically reduces total wastewater discharge；
(3) formaldehyde pollutants are transformed into other innocuous substances and are eliminated pollution factor by the present invention, realize working environment
Promotion, improve the occupational health condition of operating staff.
Detailed description of the invention
Fig. 1 is the formaldehyde separation equipment and process flow chart of butanol purifying technique.
Specific embodiment
A specific embodiment of the invention does specific statement by embodiment.
Embodiment:
A kind of formaldehyde separation method of butanol purifying technique, capital equipment include: butanol lightness-removing column 1, butanol water process tower 2, fourth
Alcohol product tower 3, methanol distillation column 4 chromatograph device 5, and the first backflash 6, the second backflash 7, reaction tank 8, reaction tank 9, waste water is temporary
Deposit pond 10, waste water scratch pool 11, the first plate filter 12, the second plate filter 13, the first collection bucket 14, the second collection bucket
15, tower reactor pump 16, feed preheater 17, the first condenser 18, the first reflux pump 19, the first cooler 20, the first reboiler 21,
Second reboiler 22, the second cooler 23, third reboiler 24, the second reflux pump 25, the second condenser 26, third cooler
27, the 4th reboiler 28, the first conveying pump 29, the first sludge pump 30, the second conveying pump 31, the second sludge pump 32, the 4th is cooling
Device 44.Each equipment is connected by respective lines.
Process flow, as shown in Figure 1, it is de- to initially enter butanol after the preheating of feed preheater 17 for raw material butanol solution 33
Light tower 1 carries out rectifying separation, and tower top feed liquid is mainly the mixture of light component methanol, propyl alcohol and a small amount of butanol and water, through the
Enter the first backflash 6 after the condensation of one condenser 18, condensate liquid takes out from the first backflash 6, pressurizes by the first reflux pump 19
Afterwards, a part is sent to the tower top of butanol lightness-removing column 1 as reflux, and another part light component material is sent through connecting pipeline 40 to methanol
Recovery tower 4 is adopted away.The kettle material of butanol lightness-removing column 1 is through connecting pipeline 34 by 16 pressurization of tower reactor pump and through 17 He of feed preheater
It is sent after first cooler 20 is cooling to chromatography device 5 and chromatographs multi_layer extraction.
The light component material of 1 tower top of butanol lightness-removing column send to 4 rectifying of methanol distillation column through connecting pipeline 40 and recycles methanol, tower
Top material enters the second backflash 7 after the condensation of the second condenser 26, and after the pressurization of the second reflux pump 25, a part is sent to first
The tower top of alcohol recovery tower 4 is produced as reflux, another part overhead condensation liquid 41 as methanol product.The tower of methanol distillation column 4
Kettle material is sent out through the second cooler 23 as fusel oil.
Chromatography 5 upper layer butanol phase solution of device is directly entered butanol product tower 3 and carries out rectifying, and tower top is butanol-water azeotrope,
Direct gas phase is sent into butanol lightness-removing column 1, and tower middle and lower part material is adopted after the 4th cooler 44 is cooling as high-purity butanol product
Out.In addition, accomplished continuously or intermittently fusel oil groove is sent in a small amount of extraction to 3 kettle material of butanol product tower after third cooler 27 is cooling,
Tower reactor is maintained to recombinate balance-dividing.
The lower water of chromatography device 5 mixes the formaldehyde components brought into liquid enrichment raw material, into 2 rectifying of butanol water process tower
Butanol therein is recycled, tower top is that butanol-water azeotrope gas phase is sent into butanol lightness-removing column 1, and tower reactor is enriched the aqueous solution of formaldehyde,
Directly sent with hot water conditions to the reaction tank of water containing aldehyde 8.Reaction tank 8 and reaction tank 9 are two identical series in parallel, when wherein one
When a series is in reactiveness, another series of reception water containing aldehyde, then switching uses the continuity for guaranteeing production.Below with
Water containing aldehyde enters reaction tank 8 to describe.
When 8 liquid level of reaction tank reaches setting value, water containing aldehyde switches to reaction tank 9.Then, electricity is added into reaction tank 8
Rock ballast material 45 starts agitating device, carbide slag is allowed to be completely dissolved in hot water.Meanwhile appropriate steam is supplemented to reaction tank 8
(LS) pond temperature is maintained to blast compressed air (OA) at 80-90 DEG C, and to reaction tank.After reaction carries out 3 hours, it is analyzed to identify
When content of formaldehyde is lower than 30mg/L in reaction tank 8 stop that supplement steam (LS) is added and stopping blasts compressed air (OA), starts
First conveying pump 29 send the low qualified water of content of formaldehyde to waste water scratch pool 10, then send via waste pipe 48 to downstream wastewater
Treatment stations.The mud of 8 bottom deposit of reaction tank, the first sludge pump 30 of starting are sent to the first plate filter 12, cross filter residue through the
One collection bucket 14 is seen off, and filtrate is sent to waste water scratch pool 10.The mud of 10 bottom of waste water scratch pool enrichment is sent to the first sludge pump
30 are separated by filtration via the first plate filter 12.
Match with reaction tank 9 is waste water scratch pool 11, the second plate filter 13, the second collection bucket 15, second send
Water pump 31 and the second sludge pump 32 constitute another series switching and use.
34 be 1 tower reactor of butanol lightness-removing column and chromatography 5 connecting pipeline of device；35 be chromatography device 5 and 3 connecting tube of butanol product tower
Line；36 be chromatography device 5 and 2 connecting pipeline of butanol water process tower；37 be to produce after the 4th cooler 44 is cooling as high-purity butanol
Product produce pipeline；38 be to produce pipeline after third cooler 27 is cooling；39 be butanol lightness-removing column 1 and 3 connecting tube of butanol product tower
Line；40 be butanol lightness-removing column 1 and 4 connecting pipeline of methanol distillation column；42 be to send after the second cooler 23 is cooling as fusel oil
Pipeline out；43 be butanol water process tower 2 and 9 connecting pipeline of reaction tank 8 and reaction tank；46 be waste water scratch pool 10 and reaction tank 8
Connecting pipeline；47 be 9 connecting pipeline of waste water scratch pool 11 and reaction tank；48 be 11 waste water of waste water scratch pool 10 and waste water scratch pool
Export pipeline.
The above disclosure is only the preferred embodiments of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, those skilled in the art can understand all or part of the processes for realizing the above embodiment, and wants according to right of the present invention
Made equivalent variations is sought, is still belonged to the scope covered by the invention.
Claims (3)
1. a kind of formaldehyde separation method of butanol purifying technique, which is characterized in that raw material butanol solution 33 is through feed preheater 17
After preheating, carry out rectifying separation into butanol lightness-removing column 1, main light component methanol, propyl alcohol and a small amount of butanol and water it is mixed
Object distillation is closed to tower top, kettle material is through connecting pipeline 34 by 16 pressurization of tower reactor pump and through feed preheater 17 and the first cooler
It is sent after 20 coolings to chromatography 5 multi_layer extraction of device；Chromatography 5 upper layer butanol phase solution of device is directly entered butanol product tower 3 and carries out rectifying,
Obtain butanol product；Chromatography 5 lower water of device mixes the formaldehyde components brought into liquid enrichment raw material, into butanol water process tower 2
Butanol therein is recycled in rectifying；2 tower top of butanol water process tower is butanol-water azeotrope, and gas phase is sent into butanol lightness-removing column 1, tower reactor
It is enriched the aqueous solution of formaldehyde, is directly sent with hot water conditions to the reaction tank of water containing aldehyde 8；When 8 liquid level of reaction tank reaches setting value,
Water containing aldehyde switches to reaction tank 9, and carbide slag material 45 is then added into reaction tank 8, and starting stirring allows carbide slag sufficiently to dissolve
In hot water, meanwhile, appropriate steam (LS) is supplemented to maintain pond temperature at 80-90 DEG C to reaction tank 8, and in time to reaction tank
8 blast compressed air (OA), oxidize the formaldehyde into formic acid, and formic acid is dissolved in the calcium hydroxide of water generation with the carbide slag of addition again
Neutralization reaction occurs, generates calcium formate and achievees the purpose that separation abjection formaldehyde.
2. the formaldehyde separation method of butanol purifying technique according to claim 1, which is characterized in that the reaction tank 8
It is two identical series in parallel with reaction tank 9, when one of them is in reactiveness, another receives water containing aldehyde, then
Switching uses guarantee continuous production.
3. the formaldehyde separation method of butanol purifying technique according to claim 1, which is characterized in that pass through oxidation reaction point
It leaves away except formaldehyde components, chemical equation is as follows:
。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201910417826.0A CN110092711A (en) | 2019-05-20 | 2019-05-20 | A kind of formaldehyde separation method of butanol purifying technique |
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| CN201910417826.0A CN110092711A (en) | 2019-05-20 | 2019-05-20 | A kind of formaldehyde separation method of butanol purifying technique |
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Cited By (3)
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| CN111848346A (en) * | 2020-08-20 | 2020-10-30 | 北京石油化工工程有限公司 | System and method for recycling n-butanol from BDO device waste liquid |
| CN114276214A (en) * | 2021-12-10 | 2022-04-05 | 湖北宜化化工股份有限公司宜都分公司 | Production method for producing pentaerythritol by recycling carbide slag |
| CN115536491A (en) * | 2021-09-30 | 2022-12-30 | 湖北宜化化工科技研发有限公司 | Production method for producing trimethylolpropane by recycling carbide slag |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848346A (en) * | 2020-08-20 | 2020-10-30 | 北京石油化工工程有限公司 | System and method for recycling n-butanol from BDO device waste liquid |
| CN115536491A (en) * | 2021-09-30 | 2022-12-30 | 湖北宜化化工科技研发有限公司 | Production method for producing trimethylolpropane by recycling carbide slag |
| CN115536491B (en) * | 2021-09-30 | 2024-04-12 | 湖北宜化化工科技研发有限公司 | Production method for producing trimethylolpropane by recycling carbide slag |
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