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Method for treating high-concentration isobutylene wastewater through PO by-product TBA pyrolysis

A technology for concentrated wastewater and isobutylene, which is used in natural water treatment, heating water/sewage treatment, and water/sewage multi-stage treatment, etc., can solve the problems of long treatment process, high equipment cost, uneconomical and other problems, and achieve low wastewater treatment cost. , The process is simple, no secondary pollution effect

Active Publication Date: 2017-01-18
WANHUA CHEM GRP CO LTD
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Problems solved by technology

The wastewater produced by methanol cracking to produce dimethyl ether also contains high-concentration organic compounds. The Chinese published patent CN101376550 uses distillation to divide the wastewater into two streams of wastewater rich in organic matter and waste water poor in organic matter, and then membrane Separation and recovery of organic matter, biochemical treatment of lean wastewater, etc. The above wastewater treatment methods have certain applicability for the treatment of high-concentration wastewater from PO by-product TBA cracking to isobutene, but the treatment process is long and costly, and it is difficult to achieve wastewater treatment. Reuse of useful substances
[0006] Wet oxidation is also an effective method for treating high-concentration organic wastewater. It has high treatment efficiency and rarely causes secondary pollution, but it needs to be carried out under high temperature and high pressure conditions, and catalysts loaded with precious metals are used. The intermediate products are often organic acids. It has a certain poisoning effect and affects the catalytic life. At the same time, it has high requirements for equipment materials, high temperature resistance, high pressure resistance, and corrosion resistance. Therefore, the equipment cost is large and the one-time investment of the system is high; It is carried out under high temperature and high pressure conditions, so it is only suitable for small flow and high concentration wastewater treatment, and it is very uneconomical for high concentration and large volume wastewater
[0007] In view of the shortcomings of the above existing alcohol-to-olefin wastewater treatment and the characteristics of PO by-product TBA cracking to isobutene wastewater, it is urgent to develop a method to solve the above deficiencies in the prior art, make full use of propylene oxide by-product tert-butanol resources, and avoid Wastewater treatment affects production, improves dehydration efficiency, simplifies wastewater treatment process, and reduces production costs

Method used

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  • Method for treating high-concentration isobutylene wastewater through PO by-product TBA pyrolysis

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] Weigh 1.83g of ruthenium nitrate and dissolve it in 1L of water, add 5.0g of niobium pentoxide and 116.7g of titanium dioxide, stir continuously for 20min, add sodium hydroxide to adjust the pH to 9, heat to 60°C and stir continuously for 4h, wash the slurry by centrifugation for 3 times, Dry at 110°C for 10h, roast at 400°C for 5h, and then use a mixed gas of 40v% hydrogen and 60v% nitrogen (with a space velocity of 100h -1 ) was reduced and activated at 400°C for 15 hours to prepare a hydrogenolysis catalyst containing 0.48wt% ruthenium, wherein the weight ratio of Nb:Ti was 1:20.

[0035] Such as figure 1 As shown, the 100mL catalyst prepared above was loaded into a fixed bed reactor with a pressure of 3Mpa and a space velocity of 35h -1, under the condition of 200°C, the COD content of stream a (source: bottom liquid after TBA cracking by-product of PO plant of Wanhua Chemical Group Co., Ltd., pH=5.3, T=126°C) is 93,400 ppm, of which 1.95wt% of alcohols, 0.92wt% o...

Embodiment 2

[0037] Weigh 1.69g of ruthenium nitrate and dissolve it in 1L of water, add 5.0g of niobium pentoxide and 175.1g of titanium dioxide, stir continuously for 20min, add sodium hydroxide to adjust the pH to 9, heat to 60°C and stir continuously for 4h, wash the slurry by centrifugation for 3 times, Dry at 110°C for 10h, roast at 400°C for 5h, and then use a mixed gas of 40v% hydrogen and 60v% nitrogen (space velocity 80h -1 ) was reduced and activated at 400°C for 12h to prepare a hydrogenolysis catalyst containing 0.3wt% ruthenium, wherein the weight ratio of Nb:Ti was 1:30.

[0038] Fill the 100mL catalyst prepared above into a fixed-bed reactor with a pressure of 2.0Mpa and a space velocity of 20h -1 , under the condition of 150°C, the COD content of stream a (source: bottom liquid after TBA pyrolysis by-product of PO plant of Wanhua Chemical Group Co., Ltd., pH=5.7, T=134°C) is 35,700PPm, of which 0.81wt% of alcohols, 0.35wt% of ethers, 0.42wt% of esters, 0.05wt% of aldehyde...

Embodiment 3

[0040] Weigh 3.93g of ruthenium nitrate and dissolve it in 1L of water, add 10.0g of niobium pentoxide and 116.7g of titanium dioxide, stir continuously for 20min, add sodium hydroxide to adjust the pH to 9, heat to 60°C and stir continuously for 4h, wash the slurry by centrifugation for 3 times, Dry at 110°C for 10h, roast at 400°C for 5h, and then use a mixed gas of 40v% hydrogen and 60v% nitrogen (with a space velocity of 120h -1 ) was reductively activated at 400°C for 17h to prepare a hydrogenolysis catalyst containing 0.97wt% ruthenium, wherein the weight ratio of Nb:Ti was 1:10.

[0041] Pack the 100mL catalyst prepared above into a fixed bed reactor with a pressure of 1.1Mpa and a space velocity of 50h -1 , under the condition of 175°C, the COD content of stream a (source: bottom liquid after TBA cracking by-product of PO plant of Wanhua Chemical Group Co., Ltd., pH=6.4, T=123°C) is 61,700PPm, of which 1.17wt% of alcohols, 0.63wt% of ethers, 0.74wt% of esters, 0.05wt%...

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Abstract

The invention provides a method for treating high-concentration isobutylene wastewater through PO by-product TBA pyrolysis. The method comprises the steps that a hydrogenolysis method is adopted to decompose ethers and esters decomposition into alcohol compounds, alcohol is produced by utilizing aldehyde ketone, saturated alkane is generated through olefin hydrogenation, the COD in the wastewater drops to be below 500 PPm by utilizing the characteristics that micromolecular alcohol and water are azeotropic, macromolecular alcohol and alkane are insoluble in water through means such as flash, poly condensation and separation and is up to the direct emissions standards after being subjected to biochemical treatment. The method is economic and high in treatment efficiency.

Description

technical field [0001] The invention relates to a method for treating waste water, in particular to a method for treating high-concentration isobutylene waste water produced by cracking PO (propylene oxide) by-product TBA (tert-butanol). [0002] technical background [0003] Isobutylene is an important chemical raw material, which is used to synthesize polyisobutylene rubber, butyl rubber, and the main monomer of isoprene. It is also widely used as medicine, pesticide, antioxidant, synthetic high-grade lubricating oil, gasoline additive and other Raw materials for fine chemical products. [0004] The PO co-oxidation method produces a large amount of tert-butanol by-product, which provides stable raw material support for the process of tert-butanol cracking to produce isobutene, but because the process of the co-oxidation method is very complicated, a large amount of impurities will be produced while the by-product tert-butanol , including alcohols, esters, aldehydes and ket...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C02F9/10B01J23/648B01J23/652C02F103/36
CPCB01J23/002B01J23/6482B01J23/6484B01J23/652B01J23/6527C02F1/06C02F1/52C02F9/00C02F2103/36
Inventor 王中华袁帅何岩刘振峰黄少峰董龙跃吕艳红黎源张本才刘阳
Owner WANHUA CHEM GRP CO LTD
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