CN1083802A - A kind of methanol sewage treatment technology - Google Patents
A kind of methanol sewage treatment technology Download PDFInfo
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- CN1083802A CN1083802A CN 93112053 CN93112053A CN1083802A CN 1083802 A CN1083802 A CN 1083802A CN 93112053 CN93112053 CN 93112053 CN 93112053 A CN93112053 A CN 93112053A CN 1083802 A CN1083802 A CN 1083802A
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- methyl alcohol
- residual liquid
- methanol
- distillation residual
- 15mpa
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Abstract
A kind of methanol sewage treatment technology; Natural gas via converter, nickel accelerant effect are forced into 15MPa with the compressed machine of water vapor generation synthetic gas down and deliver to synthetic tower under 270 ℃, 15MPa, under the effect of copper Zinc catalysts, generate methyl alcohol, after rectifying gets methyl alcohol, distillation residual liquid recycles as the raw material of producing methyl alcohol in 0.25MPa, 115-130 ℃ send into 950 ℃-1100 ℃, the roasting kiln of 0.25MPa down after the vaporization again.The present invention is applicable to the processing that contains methyl alcohol sewage of factories such as producing beer, liquor, ethanol, methyl alcohol.
Description
The present invention relates to a kind of methanol sewage treatment technology.
The industrial sewage that contains methyl alcohol can cause multiple diseases such as human eye loses one's sight, can not cure, therefore can not directly enter the river, the river, marine, the methanol sewage treatment technology that generally adopts is the biochemical processing process of Liaoning Province petrochemical complex ruleization designing institute design at present, this technology is that the sewage that contains methyl alcohol is delivered to sewage work, carry out earlier after acid-base neutralisation reaches neutrality, deliver to contact oxidation tower again, be placed with in this tower by human excrement cultured microorganism bacterial classification, (25-30 ℃) at a certain temperature, this microbial strains absorb to be decomposed methyl alcohol, then thin up by already made discharge of pipes to three class marine sites.
In addition, scientific circles are common to be thought, contains the distillation residual liquid composition more complicated of methyl alcohol, can not be recycled in the unstripped gas unstripped gas as synthesizing methanol, transforms nickel accelerant and synthetic copper Zinc catalysts catalyst effect reduces otherwise can make, and promptly can make poisoning of catalyst.
Utilize biochemical treatment to contain the method for methyl alcohol sewage, its shortcoming is:
(1) microbial strains is difficult to cultivate,
(2) construction investment cost height, one-time investment surpasses 2,100,000 yuan,
(3) technological operation is too complicated, inapplicable,
(4) the methyl alcohol sewage disposal is not thorough, and COD reaches at 60 o'clock and is discharged in the seawater, and (national standard is 3-5COD, and COD is an oxygen-consumption) still can polluted seawater,
(5) when the factory microbial strains can not cultivated, methyl alcohol sewage is discharged in the seawater after also getting thin up.
Because the above-mentioned shortcoming of biochemical treatment methyl alcohol sewage method, make this kind method at home factory seldom adopt.
Purpose of the present invention is again in a kind of above-mentioned defective that has overcome prior art is provided, both handled and contained methyl alcohol sewage without microbial strains, neither directly enter river, river, marine with containing methyl alcohol sewage, but will contain methyl alcohol sewage through handling methanol sewage treatment technology as the partial raw gas of synthesizing methanol.
The present invention is achieved in that it is with Sweet natural gas (CH
4) under 850 ℃ situation, generate synthetic gas (CO+H through transforming roasting kiln, regenerative furnace, converter (nickel accelerant is housed) with water vapor acting
2, the CO of a little
2+ N
2Deng) send into gas holder, compressor is extracted out synthetic gas by gas holder and is pressurized to 15MPa, deliver in the synthetic tower, under 270 ℃, 15MPa pressure, under the effect of copper Zinc catalysts, generate thick methyl alcohol, thick methyl alcohol gets methanol product and distillation residual liquid through rectifying, distillation residual liquid is at 0.25MPa, 115-130 ℃ down after the vaporization, sends in 950 ℃-1100 ℃, the conversion roasting kiln of 0.25MPa again, uses as the part material of producing methyl alcohol.
In the thick methyl alcohol except that containing methyl alcohol, also contain ethers and water etc., during thick methanol rectification, ethers is evaporated when temperature is lower than 64.5 ℃, and temperature makes the methyl alcohol evaporation in the time of 64.5 ℃, and rectification temperature is lower than 100 ℃, makes moisture content be difficult to evaporate and stay in the distillation residual liquid, also contain 1% methyl alcohol in the distillation residual liquid, so distillation residual liquid is also referred to as methyl alcohol sewage.
When reactive system alkalescence is strong, can produce solid sodium methylate throw out, and when acid can etching apparatus when strong, be 7-9 so distillation residual liquid preferably keeps pH value, before the distillation residual liquid vaporization, add appropriate amount of acid or alkali accent pH value is 7-9.
Distillation residual liquid is transported to the conversion roasting kiln by vaporising device (steam boiler, pipeline etc.) after vaporizing, so-called transform roasting kiln be earlier with fuel with this stove heat temperature raising to 1100 ℃, when natural vapour etc. is reduced to 950 ℃ by the back temperature, use fuel heat temperature raising to 1100 ℃ again, all the time maintain 950 ℃-1100 ℃ so transform furnace temperature, and methyl alcohol can be decomposed into CO+H in the time of 600 ℃
2So the steam of working as the distillation residual liquid vaporization enters and transforms in the roasting kiln, can make methanolysis is CO+H
2
Owing to the element of the poisoning of catalyst that makes synthesizing methanol such as sulphur etc. have been removed through operations such as desulfurization before synthetic, and the distillation residual liquid of thick methyl alcohol obtains when being synthesizing methanol, do not introduce other harmful element, so be conveyed into after the distillation residual liquid vaporization and transform roasting kiln, can not make poisoning of catalyst as reaction raw materials.
Advantage of the present invention is:
(1) overcome the distillation residual liquid of system methyl alcohol in the prior art, can make poisoning of catalyst and can not be circulated to the technology prejudice of using in the reaction raw materials, with being conveyed in the reactor feed gas after the distillation residual liquid vaporization, promptly saved reaction raw materials, overcome the pollution of methyl alcohol sewage again.
(2) since methyl alcohol sewage be used as reaction raw materials and be utilized again, and do not enter the river, river, marine, the pollution of having effected a radical cure methyl alcohol sewage.
(3) because the recycling of distillation residual liquid, 7000 tons of annual recyclable soft water reclaim 50 tons of methyl alcohol, 100,000 yuan at a discount.
(4) treatment process of this kind methyl alcohol sewage only needs to increase vaporising device (steam boiler, pipeline etc.) and biochemical sewage treatment process than (2,110,000 yuan of one-time investments), its expense only be its 1/10.
(5) processing method is simple, and is easy to operate.
Introduce specific embodiments of the invention below:
Sweet natural gas (the CH that will handle through operations such as desulfurization
4) be conveyed in 1100 ℃ the conversion roasting kiln, the distillation residual liquid of being produced methyl alcohol early stage also is conveyed into by vaporising device-steam boiler, pipeline after vaporization again and transforms roasting kiln to make the methanolysis in the boil-off gas be CO and H
2, again with above-mentioned gas mixture by behind the regenerative furnace, be conveyed into and be equipped with in nickel accelerant, 850 ℃ the converter, make natural (CH
4) generate synthetic gas (CO+H with steam reaction
2); Again above-mentioned synthetic gas is sent into gas holder, compressor is extracted out synthetic gas by gas holder and is pressurized to 15MPa, delivers in the synthetic tower unconverted CO+H in the reaction in early stage
2Also circulation is conveyed into synthetic tower, in the synthetic tower, under 270 ℃, 15MPa pressure, under the effect of copper Zinc catalysts, generate thick methyl alcohol, thick methyl alcohol gets methanol product and distillation residual liquid through rectifying, and distillation residual liquid is after removing ether, acid-base neutralisation processing, (PH=7-9), after 0.25MPa, 125.5 ℃ times vaporizations, send into 1100 ℃ again, in the conversion roasting kiln of 0.25MPa, making methanolysis is CO+H
2, and use as the part material of producing methyl alcohol.
Table 1 is thick methanol rectification gained distillation residual liquid, after the vaporization evaporation, and the analysis report of methanol content in the gained raffinate (Shenyang City's environmental protection Science Institute assay), analytical procedure: colorimetric, capacity.As seen test-results contains the distillation residual liquid of methyl alcohol, most of methyl alcohol can be evaporated through vaporization, and the treated partial raw gas that can be used as uses.
Table 1: distillation residual liquid methanol content analysis report
| Concentrate and steam % | Methanol content mg/l in the raffinate |
| 0 | 233333.3 |
| 30 | 70.0 |
| 50 | 65.0 |
| 70 | 40.0 |
| 90 | 15.0 |
Table 2 is that distillation residual liquid reclaims through vaporization, and during as part material, the gas composition analysis of unstripped gas comprises the CH that is conveyed in the unstripped gas
4, also comprise after distillation residual liquid is vaporized entering the conversion roasting kiln, by the CO+H that methanolysis generated
2, what data reflected is the composition that does not enter the preceding unstripped gas of converter that nickel accelerant is housed, and from data analysis as can be seen, does not contain the obnoxious flavour that can make poisoning of catalyst in the unstripped gas.
Table 3: be the synthetic gas gas composition analysis, promptly enter the copper Zinc catalysts is housed synthetic tower before and after gas composition analysis (comprise the early stage unreacted CO+H
2, re-enter synthetic tower by the recycle pump circulation, from data as can be seen, gaseous constituent does not contain the obnoxious flavour that can make poisoning of catalyst.
Table 4 is product quality inspection report (check of chemical fertilizer product quality supervision and inspection station, Jilin Province), be about to distillation residual liquid and handle the back makes methyl alcohol as the reactive moieties raw material survey report, as seen, the distillation residual liquid that will contain methyl alcohol is handled the back as the part material of producing methyl alcohol, does not influence the quality of methanol product.
Claims (1)
1, a kind of methanol sewage treatment technology comprises: the natural gas via converter is at 850 ℃, and the nickel accelerant effect is descended and steam reaction generates synthetic gas-CO+H
2, compressor is extracted synthetic gas out and is pressurized to 15MPa and delivers in the synthetic tower under 270 ℃, 15MPa pressure generate thick methyl alcohol under the effect of copper Zinc catalysts, and thick methyl alcohol is made methanol product through rectifying again, it is characterized in that:
Distillation residual liquid is at 0.25MPa, 115-130 ℃ down after the vaporization, sends in 950 ℃-1100 ℃, the roasting kiln of 0.25MPa again, and the part material of making to produce methyl alcohol uses.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93112053 CN1083802A (en) | 1993-07-06 | 1993-07-06 | A kind of methanol sewage treatment technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93112053 CN1083802A (en) | 1993-07-06 | 1993-07-06 | A kind of methanol sewage treatment technology |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1083802A true CN1083802A (en) | 1994-03-16 |
Family
ID=4989796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93112053 Pending CN1083802A (en) | 1993-07-06 | 1993-07-06 | A kind of methanol sewage treatment technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1083802A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100391862C (en) * | 2004-12-21 | 2008-06-04 | 哈尔滨工程大学 | Recovery of alcohol diisopropylamine from waste liquid of pharmaceutical industry |
| CN100486920C (en) * | 2006-10-16 | 2009-05-13 | 西安长庆科技工程有限责任公司 | Gas field methanol sewage disposal process |
| CN1994936B (en) * | 2006-12-05 | 2011-06-29 | 南开大学 | Method for processing and resuing carbinol waste water for circulated cooling water |
-
1993
- 1993-07-06 CN CN 93112053 patent/CN1083802A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100391862C (en) * | 2004-12-21 | 2008-06-04 | 哈尔滨工程大学 | Recovery of alcohol diisopropylamine from waste liquid of pharmaceutical industry |
| CN100486920C (en) * | 2006-10-16 | 2009-05-13 | 西安长庆科技工程有限责任公司 | Gas field methanol sewage disposal process |
| CN1994936B (en) * | 2006-12-05 | 2011-06-29 | 南开大学 | Method for processing and resuing carbinol waste water for circulated cooling water |
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| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |