CN109052338A - A kind of processing method of the Waste Sulfuric Acid of alkylation production process discharge - Google Patents
A kind of processing method of the Waste Sulfuric Acid of alkylation production process discharge Download PDFInfo
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- CN109052338A CN109052338A CN201810994438.4A CN201810994438A CN109052338A CN 109052338 A CN109052338 A CN 109052338A CN 201810994438 A CN201810994438 A CN 201810994438A CN 109052338 A CN109052338 A CN 109052338A
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- Prior art keywords
- sulfuric acid
- waste sulfuric
- alkylation
- processing method
- production process
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/905—Removal of organic impurities
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
Abstract
Disclosed in this invention is a kind of processing method of the Waste Sulfuric Acid of alkylation production process discharge, the status that the Waste Sulfuric Acid environmental hazard discharged mainly for sulfuric acid process alkylation process is significant, processing difficulty is big, cost of disposal is high, propose it is a kind of first by Waste Sulfuric Acid organic impurities oxidation method handle, the volatile component removing of the small molecule that oxidative degradation is formed, finally recycle the method that oleum or sulfur trioxide is added to reduce the water content in treated sulfuric acid so that treated sulfuric acid can direct reuse in alkylation production process.Waste Sulfuric Acid is recycled directly back in alkylation production process by low energy consumption operating methods such as oxidative degradation organic impurities, removing oxidation product and sulfur trioxide water removals, avoids the spent acid burning disposal process of high energy consumption by technology of the present invention.The technique can utilize original device, in the case where investment is little, significantly reduces the processing cost of Waste Sulfuric Acid, obtain preferable economic benefit and environmental benefit.
Description
Technical field
The present invention relates to the process fields of Waste Sulfuric Acid, and in particular to a kind of place of the Waste Sulfuric Acid of alkylation production process discharge
Reason method.
Background technique
With being gradually increased for environmental protection pressure, environmental requirement is increasingly strict, and China is gradually promoted to the finished products such as gasoline oil
Standard requirements are measured, are dressed to European Union member countries, the impurity element for having pollution in the product oils such as gasoline to environment is constantly reduced.
Different motor petrol Comparison of standards tables
| Project | State IV | State V | State VI |
| Benzene content (volume fraction)/% is not more than | 1.0 | 1.0 | 0.8 |
| Arene content (volume fraction)/% is not more than | 40 | 40 | 35 |
| Olefin(e) centent (volume fraction)/% is not more than | 28 | 25 | 18 |
| Manganese content (volume fraction)/% is not more than | 0.008 | 0.002 | 0.002 |
From the point of view of the standard evolution trend of China's motor petrol, the addition of additive is with environmentally friendly upgrading in home-produced fuel
It is gradually prohibited from using, the following content that Benzene In Gasoline, aromatic hydrocarbons and alkene how are reduced under the premise of not applicable additive is come
The quality for promoting China's gasoline becomes the main target of gasoline production quotient.Alkylate oil is using low-carbon alkene and iso-butane strong
Reaction generates trimethylpentane isomers under acid catalysed conditions, have octane number is high, the capability of antidetonance is good, steam forces down, sulfur-bearing is few,
The features such as aromatic-free and alkene is ideal clean gasoline blending component.Currently, in China's blended gasoline composition, catalysis
Cracking gasoline accounts for 73%, and catalytic reforming gasoline accounts for 15%, and alkylate oil accounts for 0.2%~0.5%.It is split due to being catalyzed in domestic gasoline
It is larger to change gasoline proportionality, causes olefin(e) centent in product oil high, gasoline upgrade cost is high, difficulty is big；In developed regions such as America and Europes,
Alkylate oil is higher in gasoline blend component proportion, and the U.S. is 12.5%~15%, and Europe is 6%~7%.Therefore, make
For the ideal blending component of clean gasoline, alkylate oil becomes unique direction of high-quality gasoline, and with environmental requirement
It improves, the increase of alkylate oil demand, alkylation process can increasingly be incremented by.
Acid concentration is 90% or so in waste sulfuric acid from alkylation, containing a large amount of organic impurities, has penetrating odor and strong corruption
Corrosion belongs to dangerous liquid waste, and processing difficulty is big, becomes the biggest obstacle for restricting alkylation process.Currently, comparative maturity
The processing mode of waste sulfuric acid from alkylation is high temperature pyrolytic cracking (HTP), can thoroughly solve the problems, such as the sulphur such as spent acid and sour gas, technique
Mainly there are 2 kinds: 1. E.I.Du Pont Company SAR technology (double conversion double absorption acid-making process, the country are commonly called as dry method), 2. Top's rope company WSA skill
Art (country is commonly called as wet process).But high temperature pyrolysis processing load is big, equipment corrosion is strong, operating cost is high, seriously affects alkyl
Change the treating capacity of Waste Sulfuric Acid.
In terms of the processing about waste sulfuric acid from alkylation, relevant patent has very much, wherein by different oxidizing
Removal waste sulfuric acid from alkylation in organic matter patented technology mainly have Chinese patent CN201611093369.7,
CN201611092684.8, CN201510946095.0 etc..These patent processing methods are single, and only by having in Waste Sulfuric Acid
Machine object is reduced or is removed, and is failed to promote treated acid concentration, be cannot achieve the route for returning to alkyl plant recycling.
This patent proposes that a kind of processing method of the Waste Sulfuric Acid of novel alkylation production process discharge, the novelty of this method are
Remove Waste Sulfuric Acid in organic matter while can also by other means promotion processing after sulfuric acid concentration, reach alkyl makeup
The application requirement set realizes the recycling of waste sulfuric acid from alkylation.This method avoid the spent acid burning disposals of high energy consumption
Process.The processing cost that Waste Sulfuric Acid can be significantly reduced obtains preferable economic benefit and environmental benefit, has boundless answer
Use prospect.
Specific embodiment
Addition oxidant is oxidized to organic part therein small in the waste sulfuric acid from alkylation that organic impurity content is 3.6%
The small molecule being oxidized to is carried out stripping removal in stripping fluid or distillation removes, is eventually adding oleum by molecular substance
Moisture in acid or sulfur trioxide reduction system, reaches acid concentration required for alkyl plant.Using acid base titration
Method analysis the liquid concentrated sulfuric acid in acid concentration, using carbometer analysis the concentrated sulfuric acid in carbon content, using karl Fischer water
Divide the water content in analyzer analysis sulfuric acid.
Embodiment 1
5g persulfuric acid is added in 100g waste sulfuric acid from alkylation, after reacting a period of time, system is heated to 100 DEG C, leads to
Enter nitrogen to take small molecular weight impurity therein out of, 20% oleum 8g is added after cooling, it is dense lower than 2% to obtain water content
Sulfuric acid 96g.
Embodiment 2
10g chlorine dioxide is added in 100g waste sulfuric acid from alkylation, after reacting a period of time, system is heated to boil,
Fluidized state 1h is kept, 5g sulfur trioxide is added after cooling, obtains the concentrated sulfuric acid 92g that water content is lower than 2%.
It is as shown in the table for the analysis data statistics in embodiment:
| Project | Sulfuric acid concentration/% | Carbon content/% | Organic removal rate/% | Water content/% |
| Embodiment 1 | 97.5 | 1.1 | 70.67 | 1.4 |
| Embodiment 2 | 98.1 | 1.3 | 66.78 | 0.6 |
As can be seen from the table, the organic matter in Waste Sulfuric Acid can be effectively removed by the way that different oxidants are added, removed
The equal > 50% of rate, and the reduction of water content in sulfuric acid can be realized by addition oleum or sulfur trioxide, obtain high concentration,
The concentrated sulfuric acid of low content of organics realizes the recycling of waste sulfuric acid from alkylation.
Claims (5)
1. a kind of processing method of the Waste Sulfuric Acid of alkylation production process discharge, including following sequence of step:
1) oxidant is added in Waste Sulfuric Acid to carry out aoxidizing de- organic matter processing；
2) devolatilization processing is carried out to by step 1) treated Waste Sulfuric Acid；
3) oleum or sulfur trioxide is added in by step 2) treated Waste Sulfuric Acid, by free water content in Waste Sulfuric Acid
It reduces.
2. a kind of processing method of waste sulfuric acid from alkylation according to claim 1, it is characterised in that: having in Waste Sulfuric Acid
Machine impurity is removed by the method for oxidation, after the step 1) oxidation processes, organic impurities in Waste Sulfuric Acid
Removal rate is not less than 30%, and used oxidant is selected from least one of following during being somebody's turn to do: persulfuric acid, chlorine dioxide,
All types of oxidants can be used alone, and can also be combined into hybrid oxidant by different proportion group.
3. a kind of processing method of waste sulfuric acid from alkylation according to claim 2, it is characterised in that: adopted during being somebody's turn to do
Oxidant, without using can cause to be alkylated the further diluted water-containing materials of sulfuric acid.
4. a kind of processing method of waste sulfuric acid from alkylation according to claim 1, it is characterised in that: pass through step 1) institute
It states the organic impurities in oxidation processes Waste Sulfuric Acid to exist in the form of the volatile component of small molecule after aoxidizing, this part composition exists
Removed in step 2) by the method for stripping or distilling, should during used by stripping fluid in following at least
A kind of: nitrogen, carbon dioxide, air, oxygen, all types of gas mediums can be used alone, and can also pass through different proportion group
It is combined into mixing stripping fluid.
5. a kind of processing method of waste sulfuric acid from alkylation according to claim 1, it is characterised in that: pass through step 2) institute
The moisture in the Waste Sulfuric Acid of devolatilization is stated, is gone by the method for addition oleum or sulfur trioxide described in step 3)
It removes, after oleum or sulfur trioxide is added in step 3), free water content is not higher than 2% in Waste Sulfuric Acid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810994438.4A CN109052338A (en) | 2018-08-27 | 2018-08-27 | A kind of processing method of the Waste Sulfuric Acid of alkylation production process discharge |
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| CN201810994438.4A CN109052338A (en) | 2018-08-27 | 2018-08-27 | A kind of processing method of the Waste Sulfuric Acid of alkylation production process discharge |
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| CN109052338A true CN109052338A (en) | 2018-12-21 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112158809A (en) * | 2020-09-27 | 2021-01-01 | 中国石油大学(华东) | Method for treating alkylation waste sulfuric acid |
Citations (6)
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|---|---|---|---|---|
| CN86101738A (en) * | 1986-03-15 | 1987-03-25 | 刘清林 | The waste acid recycling method of sulfuric acid alkylation |
| CN1982206A (en) * | 2005-12-14 | 2007-06-20 | 催化蒸馏技术公司 | Process for regenerating spent sulfuric acid |
| 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 |
| CN104118851A (en) * | 2014-06-20 | 2014-10-29 | 马鞍山市华清环保工程有限公司 | Method for regenerating waste sulfuric acid containing high-concentration organic matters |
| CN105502309A (en) * | 2015-12-17 | 2016-04-20 | 广西大学 | Method for catalyzing alkylated waste sulfuric acid through lignocellulose ester |
| CN107792836A (en) * | 2016-08-31 | 2018-03-13 | 中国石油化工股份有限公司 | The renovation process and device of a kind of waste sulfuric acid from alkylation |
-
2018
- 2018-08-27 CN CN201810994438.4A patent/CN109052338A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86101738A (en) * | 1986-03-15 | 1987-03-25 | 刘清林 | The waste acid recycling method of sulfuric acid alkylation |
| CN1982206A (en) * | 2005-12-14 | 2007-06-20 | 催化蒸馏技术公司 | Process for regenerating spent sulfuric acid |
| 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 |
| CN104118851A (en) * | 2014-06-20 | 2014-10-29 | 马鞍山市华清环保工程有限公司 | Method for regenerating waste sulfuric acid containing high-concentration organic matters |
| CN105502309A (en) * | 2015-12-17 | 2016-04-20 | 广西大学 | Method for catalyzing alkylated waste sulfuric acid through lignocellulose ester |
| CN107792836A (en) * | 2016-08-31 | 2018-03-13 | 中国石油化工股份有限公司 | The renovation process and device of a kind of waste sulfuric acid from alkylation |
Non-Patent Citations (3)
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| 林儒等: "烷基化废硫酸的再生", 《硫酸工业》 * |
| 王少杰: "PVC生产原料乙炔净化废硫酸资源化利用技术研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 辽宁省石油化工技术情报总站: "《化工三废治理技术》", 31 December 1983 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112158809A (en) * | 2020-09-27 | 2021-01-01 | 中国石油大学(华东) | Method for treating alkylation waste sulfuric acid |
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Address after: No.57, Huaihe East Road, Qingdao Economic and Technological Development Zone, Shandong Province 266500 Applicant after: Qingdao Huicheng Environmental Protection Technology Group Co.,Ltd. Address before: No.57, Huaihe East Road, Qingdao Economic and Technological Development Zone, Shandong Province 266500 Applicant before: QINGDAO HUI CHENG ENVIRONMENTAL TECHNOLOGY Co.,Ltd. |