CN109095442B - 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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- CN109095442B CN109095442B CN201810977327.2A CN201810977327A CN109095442B CN 109095442 B CN109095442 B CN 109095442B CN 201810977327 A CN201810977327 A CN 201810977327A CN 109095442 B CN109095442 B CN 109095442B
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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
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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 hazard, 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 reducing the water content in the waste sulfuric acid and then separating the sulfuric acid from other impurity components in the waste sulfuric acid by using a freezing crystallization method. The sulfuric acid obtained by crystallization and purification can be directly reused in the alkylation production process, and the enriched impurity components are subjected to waste acid incineration treatment. According to the process technology, most of the waste sulfuric acid is directly recycled to the alkylation production process by low-energy-consumption operation methods such as sulfur trioxide dehydration, crystallization separation and impurity enrichment, so that the treatment load of a waste acid incineration device is greatly reduced. 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
With the increasing environmental protection pressure and the increasingly strict environmental protection requirements, the quality standard requirements of gasoline and other finished oil products are gradually improved in China, and the oil products are looked at the EU countries, so that the impurity elements polluting the environment in the gasoline and other finished oil products are continuously reduced.
Gasoline standard comparison table for different vehicles
| Item | National IV | National V | Country VI |
| Benzene content (volume fraction)/% is not more than | 1.0 | 1.0 | 0.8 |
| Aromatic content (volume fraction)/% of not more than | 40 | 40 | 35 |
| Olefin content (volume fraction)/% of not more than | 28 | 25 | 18 |
| Manganese content (volume fraction)/% is not more than | 0.008 | 0.002 | 0.002 |
From the standard development trend of gasoline for vehicles in China, the addition of additives in the gasoline made in China is gradually forbidden along with the upgrading of environmental protection, and how to reduce the content of benzene, aromatic hydrocarbon and olefin in the gasoline to improve the quality of the gasoline in China on the premise of not using the additives becomes the main target of gasoline manufacturers in the future. The alkylate oil is trimethyl pentane isomer produced by reaction of low carbon olefin and isobutane under the catalysis of strong acid, has the characteristics of high octane number, good antiknock performance, low steam pressure, less sulfur, no aromatic hydrocarbon and olefin and the like, and is an ideal clean gasoline blending component. At present, in the composition of blended gasoline in China, catalytic cracking gasoline accounts for 73 percent, catalytic reforming gasoline accounts for 15 percent, and alkylate oil accounts for 0.2 to 0.5 percent. The catalytic cracking gasoline in domestic gasoline has a large proportion, so that the olefin content in the finished product oil is high, and the upgrading cost and difficulty of the gasoline are high; in developed areas such as Europe and America, the proportion of the alkylate oil in gasoline blending components is higher, 12.5% -15% in the United states and 6% -7% in Europe. Therefore, alkylate is the only direction for high quality gasoline as an ideal blending component for clean gasoline, and the demand for alkylate is increasing and the alkylation process is increasing with the increasing demand for environmental protection.
The acid concentration in the alkylation waste sulfuric acid is about 90 percent, 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 alkylated waste sulfuric acid is a high-temperature pyrolysis method, the problems of sulfur such as waste acid, acid gas and the like can be thoroughly solved, and the process mainly comprises 2 types: the technology comprises the steps of firstly, SAR technology (two-conversion and two-absorption acid making technology, commonly called dry method in China) of DuPont company, and secondly, WSA technology (commonly called wet method in China) of TopuSo 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 alkylated waste acid comprises the following steps of preparing different sulfate products, such as Chinese patents 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, CN 201710468949.8; (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. These patents have high energy consumption, high investment cost, poor operability, low added value of products, and no method for separating organic matters in the alkylation waste sulfuric acid by adopting freezing crystallization is found in the above researches. The patent provides a novel processing method of waste sulfuric acid that alkylation production process discharged, and the novelty of this method lies in the thinking novelty, and the degree of crystallinity of sulphuric acid is different under according to different concentrations, adopts fuming sulfuric acid or sulfur trioxide to adjust the sulphuric acid concentration in the alkylation waste sulfuric acid, makes it separate with solid crystallization's mode and impurity under certain concentration, and the sulphuric acid after the crystallization purification can directly return alkylation unit and use. The method is simple and easy to operate, has low cost, greatly reduces the incineration load of the alkylated waste sulfuric acid, and has very wide application prospect.
Detailed Description
Adding fuming sulfuric acid or sulfur trioxide into alkylation waste sulfuric acid, reducing the water content in the waste sulfuric acid to be below 2%, adding pure sulfuric acid seed crystals, crystallizing below a condensation point corresponding to the concentration of sulfuric acid to realize separation of sulfuric acid and organic impurities, melting the crystals into liquid concentrated sulfuric acid at room temperature, analyzing the acid concentration in the liquid concentrated sulfuric acid by adopting an acid-base titration method, analyzing the carbon content in the concentrated sulfuric acid by adopting a carbon determination instrument, and analyzing the water content in the sulfuric acid by adopting a Karl Fischer moisture tester.
Example 1
The method comprises the steps of adopting 20% fuming sulfuric acid to adjust the water content in the alkylation waste sulfuric acid with the acid concentration of 91.3%, the carbon content of 3.6% and the water content of 4.5% to 1.5%, placing the adjusted alkylation waste sulfuric acid in a cold environment at the temperature of-1.5 ℃ for cooling, adding a sulfuric acid crystal seed prepared in advance into the waste acid when the temperature of a waste acid system reaches-1.5 ℃, stirring for crystallization for 1 hour, and then separating crystals from a liquid phase through a low-temperature centrifuge. The separated crystal is melted at room temperature to become concentrated sulfuric acid liquid.
Example 2
The method comprises the steps of adopting 20% fuming sulfuric acid to adjust the water content in the alkylation waste sulfuric acid with the acid concentration of 91.3%, the carbon content of 3.6% and the water content of 4.5% to 0.5%, placing the adjusted alkylation waste sulfuric acid in a cold environment at 0 ℃ for cooling, adding a sulfuric acid crystal seed prepared in advance into the waste acid when the temperature of a waste acid system reaches 0 ℃, stirring for crystallizing for 1 hour, and then separating crystals from a liquid phase through a low-temperature centrifuge. The separated crystal is melted at room temperature to become concentrated sulfuric acid liquid.
Example 3
The method comprises the steps of adjusting the water content of alkylated waste sulfuric acid with the acid concentration of 91.3%, the carbon content of 3.6% and the water content of 4.5% to 1.1% by adopting sulfur trioxide, cooling the adjusted alkylated waste sulfuric acid in a-1 ℃ cold environment, adding a sulfuric acid seed crystal prepared in advance into waste acid when the temperature of a waste acid system reaches-1 ℃, stirring and crystallizing for 1 hour, and separating crystals from a liquid phase by using a low-temperature centrifuge. The separated crystal is melted at room temperature to become concentrated sulfuric acid liquid.
Example 4
Adjusting the water content of the alkylated waste sulfuric acid with the acid concentration of 91.3%, the carbon content of 3.6% and the water content of 4.5% to 0.7% by adopting sulfur trioxide, placing the adjusted alkylated waste sulfuric acid in a cold environment at the temperature of-0.5 ℃ for cooling, adding a sulfuric acid crystal seed prepared in advance into the waste acid when the temperature of a waste acid system reaches-0.5 ℃, stirring and crystallizing for 1 hour, and separating crystals from a liquid phase by using a low-temperature centrifuge. The separated crystal is melted at room temperature to become concentrated sulfuric acid liquid.
The statistics for the analysis data in the examples are shown in the following table:
| item | Sulfuric acid concentration/%) | Carbon content/%) | Water content/% |
| Example 1 | 98.7 | 0.3 | 1 |
| Example 2 | 99.3 | 0.6 | 0.1 |
| Example 3 | 98.8 | 0.4 | 0.8 |
| Example 4 | 99.1 | 0.5 | 0.4 |
As can be seen from the data in the table, the water content in the alkylation waste sulfuric acid is reduced by adding fuming sulfuric acid or sulfur trioxide, impurity removal and purification of the waste sulfuric acid can be effectively realized in a freezing crystallization mode, concentrated sulfuric acid with high concentration and low organic matter content is obtained, and online cyclic utilization of the alkylation waste sulfuric acid can be realized.
Claims (4)
1. A method for treating waste sulfuric acid discharged in an alkylation production process comprises the following steps:
1) adding oleum or sulfur trioxide into the waste sulfuric acid to reduce the content of free water in the waste sulfuric acid;
2) cooling the dewatered waste sulfuric acid to below the condensation point of pure sulfuric acid by a freezing method, so that the sulfuric acid is separated out from a liquid phase in a solid crystal form, and simultaneously keeping a certain amount of residual liquid phase in a system;
3) separating the sulfuric acid solid crystals obtained in the step 2) from the residual liquid phase to obtain purified sulfuric acid and waste acid with concentrated impurities;
4) the purified sulfuric acid obtained in the step 3) can be returned to an alkylation device or used in other technological processes needing sulfuric acid;
5) the waste acid with concentrated impurities obtained in the step 3) can be directly sent to a waste acid incineration device to finish the treatment of the alkylation waste sulfuric acid, and the steps 1) to 3) can be repeated again, so that the concentration degree of the impurities is further improved, and the obtained sulfuric acid with enriched impurities is sent to the waste acid incineration device to finish the treatment of the alkylation waste sulfuric acid;
the water in the waste sulfuric acid is removed by adding oleum or sulfur trioxide; after fuming sulfuric acid or sulfur trioxide is added in the step 1), the free water content in the waste sulfuric acid is not higher than 2 percent;
impurities in the waste sulfuric acid are removed by a crystallization separation method; after the treatment of the step 2) and the step 3), the removal rate of impurities in the obtained purified sulfuric acid is not lower than 30%, the concentration of the impurities is not lower than 95%, and the standard of reusing the purified sulfuric acid in the alkylation production process is met.
2. The process of claim 1, wherein the process further comprises the steps of: in the step 2), the temperature of the dewatered waste sulfuric acid is reduced to generate crystal, and the temperature is not lower than-15 ℃.
3. The process of claim 1, wherein the process further comprises the steps of: the step 2) can be completed in the same equipment or can be completed in separate equipment respectively according to the temperature reduction operation in the claims and the liquid-solid separation operation in the step 3).
4. The process of claim 1, wherein the process further comprises the steps of: compared with the waste sulfuric acid directly discharged from the alkylation production process, the waste acid of the concentrated impurities fed into the waste acid incineration device in the step 5) is greatly reduced in quantity, and the impurity concentration is greatly improved; the amount of waste acid from impurity concentration is directly 50% of the waste sulfuric acid discharged from the alkylation process.
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| CN1008352B (en) * | 1986-03-15 | 1990-06-13 | 刘清林 | Recovery of waste acid of sulfuric acid alkylation |
| CN1136171C (en) * | 1999-03-09 | 2004-01-28 | 周泽川 | Integrated process using in site regenerated sulfuric acid as catalyst |
| CN102502530A (en) * | 2011-10-26 | 2012-06-20 | 瓮福（集团）有限责任公司 | Method for producing electronic-grade sulfuric acid by static fusion crystallization |
| CN108069406B (en) * | 2016-11-15 | 2019-12-13 | 中国石油化工股份有限公司 | Regeneration method of alkylation waste sulfuric acid |
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