CN108862208B - Method for treating waste sulfuric acid discharged in alkylation production process - Google Patents
Method for treating waste sulfuric acid discharged in alkylation production process Download PDFInfo
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Abstract
The invention discloses a method for treating waste sulfuric acid discharged in an alkylation production process, which mainly aims at the current situations of obvious environmental harm, large treatment difficulty and high treatment cost of the waste sulfuric acid discharged in the alkylation process of a sulfuric acid method, and provides a method for reacting the waste sulfuric acid with alumina to generate a solid product, then roasting the solid product at a temperature from low to high in sequence, removing moisture and organic impurities step by step, explaining and discharging sulfur trioxide, and absorbing the sulfur trioxide to prepare fresh sulfuric acid, thereby realizing the regeneration of the alkylation waste sulfuric acid. The process technology removes water and organic impurities by a step-by-step roasting decomposition method, realizes the regeneration of sulfuric acid by utilizing sulfur trioxide released by the decomposition of aluminum sulfate at a lower temperature, and avoids the high-temperature incineration treatment process of waste acid with high energy consumption. The process can utilize the original device, obviously reduce the treatment cost of the waste sulfuric acid under the condition of low investment, and obtain better economic benefit and environmental benefit.
Description
Technical Field
The invention relates to the field of treatment of waste sulfuric acid, in particular to a method for treating waste sulfuric acid discharged in an alkylation production process.
Background
Sulfuric acid is widely used as an important basic chemical raw material in many industrial processes, including: alkylation, nitration, esterification, sulfonation, catalysis, gas drying and the like, or the processes of titanium dioxide production, steel acid washing, gas drying and the like. Sulfuric acid is used in most of these industrial processes as a catalyst or medium and does not enter the final product, thus producing a large amount of waste sulfuric acid in these processes. Typical of these waste sulfuric acids include alkylated waste acids and titanium dioxide waste acids.
Taking the alkylation waste sulfuric acid as an example, the acid concentration is about 90%, and the alkylation waste sulfuric acid contains a large amount of organic impurities, has pungent odor and strong corrosivity, belongs to dangerous liquid waste, has high treatment difficulty, and becomes the biggest obstacle for restricting the alkylation process. At present, the mature treatment mode of the waste alkylated sulfuric acid is a high-temperature pyrolysis method, which can thoroughly solve the sulfur problems of waste acid, acid gas and the like, and the main processes of the method comprise 2 types: (1) the SAR technology (two-conversion and two-absorption acid making process, domestic common name is dry method) of DuPont company, and the WSA technology (domestic common name is wet method) of TopuSol company. But the high-temperature pyrolysis treatment load is large, the equipment corrosivity is strong, the operation cost is high, and the treatment capacity of the alkylation waste sulfuric acid is seriously influenced.
In the treatment of waste sulfuric acid from alkylation, there are many patents, which are mainly divided into three areas: (1) The method for preparing different sulfate products by using the waste acid from alkylation comprises the following steps of Chinese patents of CN201611258083.X, CN201710345627.4, CN201710010923.9, CN201510951508.4, CN201510951949.4, CN201510946136.6 and the like; (2) Pyrolyzed in different ways, such as chinese patents cn201611093229.X, CN201510346801.8, CN201610041456.1, CN201710468949.8; (3) Organic matters in the alkylation waste sulfuric acid are removed by oxidation with different oxidants, such as Chinese patents CN201611093369.7, CN201611092684.8, CN201510946095.0 and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for treating waste sulfuric acid discharged in an alkylation production process, which can obviously reduce the treatment cost of the waste sulfuric acid and obtain better economic benefit and environmental benefit.
The invention provides a method for treating waste sulfuric acid discharged in an alkylation production process, which comprises the following sequential steps:
1) Adding waste sulfuric acid into excessive alumina solid for reaction to obtain a solid intermediate product (I);
2) Carrying out low-temperature roasting treatment on the solid intermediate product (I) obtained by the treatment in the step 1) to obtain a solid intermediate product (II);
3) Carrying out high-temperature roasting treatment on the solid intermediate product (II) obtained by the treatment in the step 2) to obtain a gaseous sulfur trioxide product and an alumina solid;
4) Absorbing the gaseous sulfur trioxide product obtained in the step 3) to obtain fresh sulfuric acid;
5) Returning the alumina solid obtained in the step 3) to the step 1) to realize recycling.
In particular, in step 1), the spent sulfuric acid is reacted with alumina in a mass ratio between 0.1 and 10, preferably between 0.5 and 1, at a temperature between-5 ℃ and 250 ℃, preferably between 50 ℃ and 200 ℃, in a device with stirring or moving parts, finally obtaining the solid intermediate product (I).
Specifically, in the step 2), the solid intermediate product (I) obtained by the step 1) is roasted at a roasting temperature of between 100 and 500 ℃, preferably between 250 and 350 ℃, and the moisture and organic impurities contained in the solid intermediate product (I) obtained by the step 1) are removed from the solid material in a gas phase form in the roasting process at the present stage.
Specifically, in the step 3), the solid intermediate product (II) treated in the step 2) is roasted at a higher temperature, the roasting temperature is between 350 ℃ and 1000 ℃, preferably between 650 ℃ and 850 ℃, sulfur contained in the solid intermediate product (II) obtained by the step 2) escapes in the form of sulfur trioxide during the roasting process at this stage, the main component of the remaining solid matter is aluminum oxide, the sulfur content in the remaining solid matter is not higher than 10% by mass, and more preferably, the sulfur content in the remaining solid matter is not higher than 3% by mass.
Specifically, in step 3), 85% or more concentrated sulfuric acid, more preferably 98% or more concentrated sulfuric acid is used to absorb sulfur trioxide to obtain fuming sulfuric acid, and then the fuming sulfuric acid is diluted to obtain fresh sulfuric acid.
Specifically, from step 1) to step 5), the alumina is recycled in the processes of sulfuric acid conversion, decomposition and regeneration, and a chemical chain loop (chemical loop) is formed.
The invention has the beneficial effects that: the invention provides a novel method for treating waste sulfuric acid discharged in an alkylation production process, which creatively provides that the treatment of the waste sulfuric acid is realized by using 'chemical chain circulation' of alumina: firstly, reacting alumina with waste sulfuric acid to obtain aluminum sulfate containing impurities, wherein the impurities mainly comprise organic matters and partial moisture in the waste sulfuric acid, then enabling the crystallized water and the organic impurities in the aluminum sulfate to escape from the aluminum sulfate by a heating method at a certain temperature, finally increasing the temperature to enable the aluminum sulfate to be decomposed to generate alumina and sulfur trioxide, absorbing the sulfur trioxide obtained by decomposition to prepare fuming sulfuric acid, and finally diluting to obtain fresh sulfuric acid. The fresh sulfuric acid can not only meet the application requirements of the alkylation device, but also be applied to other chemical industries, and the cyclic regeneration and utilization of the alkylation waste sulfuric acid are realized. The method avoids the waste acid incineration treatment process with high energy consumption, can obviously reduce the treatment cost of the waste sulfuric acid, obtains better economic benefit and environmental benefit, and has very wide application prospect.
Detailed Description
1) Reacting alkylated waste sulfuric acid with aluminum oxide in a small stirring kettle according to a certain mass ratio, controlling a certain temperature and continuously stirring in the reaction process, and stopping stirring when a reaction system is viscous to solidify the reaction system; 2) Roasting the condensate in the step 1) at the temperature of 250-350 ℃; 3) Continuously roasting the sample in the step 2) at 650-850 ℃, and 1) reacting the alkylated waste sulfuric acid and the alumina in a small stirring kettle according to a certain mass ratio, controlling a certain temperature and continuously stirring in the reaction process, and stopping stirring when the reaction system is viscous to solidify the reaction system; 2) Roasting the condensate in the step 1) at the temperature of 250-350 ℃; 3) Continuing to roast the sample in the step 2) at 650-850 ℃, and absorbing the tail gas after roasting by adopting concentrated sulfuric acid with the concentration of more than 98%. And after the reaction is finished, analyzing the acid concentration in the absorbed fuming sulfuric acid by adopting an acid-base titration method according to the national standard requirements, and analyzing the chemical composition of the residual solid after roasting by adopting an X-ray fluorescence spectrometer.
Example 1
Adding 50g of alumina into 50g of waste sulfuric acid, stirring for reaction, controlling the reaction temperature to be 60 ℃, transferring the reaction material to a muffle furnace at 250 ℃ for roasting after the reaction material is solidified, continuously heating to 650 ℃ after 2 hours, keeping the temperature for 3 hours, and introducing roasting tail gas into 20g98.3% concentrated sulfuric acid for absorption.
Example 2
Adding 35g of alumina into 50g of waste sulfuric acid, stirring for reaction, controlling the reaction temperature to be 70 ℃, transferring the reaction material to a 280 ℃ muffle furnace for roasting after the reaction material is solidified, continuously heating to 700 ℃ after 2 hours, keeping the temperature for 3 hours, and introducing roasting tail gas into 20g98.3% concentrated sulfuric acid for absorption.
Example 3
Adding 20g of alumina into 30g of waste sulfuric acid, stirring for reaction, controlling the reaction temperature to be 80 ℃, transferring the reaction material to a muffle furnace at 300 ℃ for roasting after the reaction material is solidified, continuously heating to 750 ℃ after 2 hours, keeping the temperature for 3 hours, and introducing roasting tail gas into 20g98.3% concentrated sulfuric acid for absorption.
Example 4
Adding 15g of alumina into 30g of waste sulfuric acid, stirring for reaction, controlling the reaction temperature to be 90 ℃, transferring the reaction material to a 330 ℃ muffle furnace for roasting after the reaction material is solidified, continuously heating to 800 ℃ after 2 hours, keeping the temperature for 3 hours, and introducing roasting tail gas into 20g98.3% concentrated sulfuric acid for absorption.
The analytical data statistics for the examples are shown in the following table:
| item | Sulfuric acid concentration/% in the absorption solution | Al in the remaining solid 2 O 3 Content/%) | S content/% of remaining solids |
| Example 1 | 125 | 91 | 2.8 |
| Example 2 | 123 | 91.7 | 2.8 |
| Example 3 | 105 | 92.5 | 2.1 |
| Example 4 | 106 | 93.2 | 1.9 |
As can be seen from the data in the table, the regeneration treatment of the alkylation waste sulfuric acid can be realized at a lower temperature by the method of alumina 'chemical chain circulation' to obtain fresh concentrated sulfuric acid.
Claims (9)
1. A method for treating waste sulfuric acid discharged from an alkylation production process comprises the following sequential steps:
1) Adding waste sulfuric acid into excessive alumina solid for reaction to obtain a solid intermediate product (I);
2) Carrying out low-temperature roasting treatment on the solid intermediate product (I) obtained by the treatment in the step 1) to obtain a solid intermediate product (II), wherein the roasting temperature is between 100 and 500 ℃, and water and organic impurities contained in the solid intermediate product (I) obtained by the treatment in the step 1) are removed from the solid material in a gas phase form in the roasting process at the stage;
3) Carrying out high-temperature roasting treatment on the solid intermediate product (II) obtained by the treatment in the step 2) to obtain a gaseous sulfur trioxide product and an alumina solid;
4) Absorbing the gaseous sulfur trioxide product obtained in the step 3) to obtain fresh sulfuric acid;
5) Returning the alumina solid obtained in the step 3) to the step 1) to realize recycling.
2. The process of claim 1, wherein the process further comprises the steps of: reacting waste sulfuric acid with alumina at the mass ratio of 0.1-10 and-5-250 deg.c in a reactor to obtain solid intermediate product.
3. The method for treating waste sulfuric acid discharged from an alkylation production process according to claim 2, wherein: reacting waste sulfuric acid with alumina at a reaction temperature of 50-200 ℃, wherein the mass ratio of the alumina to the sulfuric acid is 0.5-1.
4. The process of claim 1, wherein the process further comprises the steps of: in the step 2), the roasting temperature for roasting the solid intermediate product (I) obtained by the step 1) is between 250 and 350 ℃.
5. The method for treating waste sulfuric acid discharged from an alkylation production process according to claim 1, wherein: in the step 3), the solid intermediate product (II) treated in the step 2) is roasted at a higher temperature, the roasting temperature is between 350 ℃ and 1000 ℃, the sulfur element contained in the solid intermediate product (II) obtained by the step 2) escapes in the roasting process at the stage in the form of sulfur trioxide, the main component of the residual solid matters is aluminum oxide, and the mass percentage content of the sulfur element in the residual solid matters is not higher than 10%.
6. A process according to claim 5, wherein the treatment of the spent sulfuric acid from the alkylation process is carried out by: in the step 3), the solid intermediate product (II) treated in the step 2) is roasted at a temperature of between 650 and 850 ℃, and the sulfur element accounts for not more than 3% by mass of the remaining solid substances.
7. The process of claim 1, wherein the process further comprises the steps of: absorbing sulfur trioxide by using over 85% concentrated sulfuric acid in the step 3) to obtain fuming sulfuric acid, and then diluting the fuming sulfuric acid to obtain fresh sulfuric acid.
8. The process of claim 7, wherein the sulfuric acid effluent from the alkylation process comprises: in step 3) more than 98% of concentrated sulfuric acid is used to absorb sulfur trioxide.
9. The method for treating waste sulfuric acid discharged from an alkylation production process according to claim 1, wherein: from step 1) to step 5), the alumina is recycled in the processes of sulfuric acid conversion, decomposition and regeneration, and a chemical chain cycle is formed.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139660A (en) * | 2007-10-08 | 2008-03-12 | 郑满秀 | Method for extracting iron-lead and gold-silver from gold concentrate acidifying baking residue |
| CN103771353A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Regeneration method for alkylated waste sulfuric acid |
| CN104944384A (en) * | 2014-03-25 | 2015-09-30 | 山东鲁北企业集团总公司 | Combined process and combined device for comprehensive utilization for chemical decomposition waste sulphuric acid and gypsum |
| CN105480998A (en) * | 2015-12-17 | 2016-04-13 | 广西大学 | Method for preparing aluminum sulfate by catalyzing alkylated waste sulfuric acid with lignocellulose ester |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139660A (en) * | 2007-10-08 | 2008-03-12 | 郑满秀 | Method for extracting iron-lead and gold-silver from gold concentrate acidifying baking residue |
| CN103771353A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Regeneration method for alkylated waste sulfuric acid |
| CN104944384A (en) * | 2014-03-25 | 2015-09-30 | 山东鲁北企业集团总公司 | Combined process and combined device for comprehensive utilization for chemical decomposition waste sulphuric acid and gypsum |
| CN105480998A (en) * | 2015-12-17 | 2016-04-13 | 广西大学 | Method for preparing aluminum sulfate by catalyzing alkylated waste sulfuric acid with lignocellulose ester |
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