CN107754850B - Method for preparing carbon-based acidic material by using alkylated waste acid containing ionic liquid - Google Patents
Method for preparing carbon-based acidic material by using alkylated waste acid containing ionic liquid Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
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- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/88—Concentration of sulfuric acid
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- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/92—Recovery from acid tar or the like, e.g. alkylation acids
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- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
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- C01C1/24—Sulfates of ammonium
- C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
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Abstract
The invention relates to a method for preparing a carbon-based acidic material by using alkylated waste acid containing ionic liquid, which comprises the following steps: heating the alkylated waste acid containing the ionic liquid auxiliary agent to 100-500 ℃, keeping for 1-10 h, washing the product to be neutral by using a solvent, and drying at 60-200 ℃ to obtain the carbon-based acidic material, wherein the solvent is at least one of water, dilute sulfuric acid, ammonia water and ammonium sulfate. The method for preparing the carbon-based acidic material has the advantages of short process route, low investment, simple operation, low operating cost and wide application range, can realize resource recycling of the ionic liquid, the acid-soluble oil and the sulfuric acid in the waste sulfuric acid, and reduces carbon emission.
Description
Technical Field
The invention relates to a method for preparing a carbon-based acidic material by using alkylated waste acid containing ionic liquid, in particular to a method for preparing a carbon-based acidic material by using waste acid generated by the reaction of isobutane and olefin under the concerted catalysis of the ionic liquid.
Technical background:
the sulfuric acid alkylation is a process for producing high-purity industrial isooctane by using butenes, isobutene or pentenes which are byproducts of catalytic cracking and catalytic reforming devices as raw materials, using 98 percent sulfuric acid as a catalyst and using a four-carbon isoparaffin and olefin through an alkylation technology. The gradual deterioration of the domestic atmospheric environment promotes the acceleration of oil upgrading, and the alkylate oil has the advantages of high octane number, low steam pressure, no sulfur, no aromatic hydrocarbon and the like, and is an ideal environment-friendly high-octane gasoline additive component for replacing MTBE and ethanol. Increasing the blending ratio of isooctane is the most effective way to accelerate the upgrade of gasoline in China, reduce the emission of harmful gas in tail gas of motor vehicles and protect the environment. Meanwhile, the holding capacity of automobiles in China is continuously increased, and the rigidity demand for high-quality oil products is sharply increased. Therefore, in the future air pollution prevention and treatment and oil quality upgrading process, the importance of isooctane is increasingly prominent, and the good market prospect of isooctane production in the petroleum refining industry of China is also indicated. At present, a concentrated sulfuric acid method is dominant in industrial production of isooctane, in recent years, newly built isooctane devices at home and abroad mostly adopt a sulfuric acid technology, and 84 percent of the newly built devices at home adopt a concentrated sulfuric acid technology. When the concentration of sulfuric acid is less than 90% during the alkylation reaction, it is discharged from the reactor, which is said alkylation waste sulfuric acid, and 80-100kg of waste sulfuric acid is produced per ton of alkylate. At present, the domestic sulfuric acid process alkylation production capacity exceeds 1000 ten thousand tons, and if the domestic sulfuric acid process alkylation production capacity reaches over 100 ten thousand tons of waste sulfuric acid.
The auxiliary agent can increase the contact surface of the sulfuric acid and the liquefied hydrocarbon, and the catalyst can be better contacted with reactants in a reactor and is in a good emulsified state, so that the reaction efficiency is improved, the octane number of a product is improved, and the consumption of the catalyst is reduced. In 2009, BalaSubramaniam first reported that the ionic liquid is used to regulate and control the alkylation reaction of isobutane/butene with liquid acid, and the product shows better alkylation catalytic activity (Journal of catalysis2009,268,243-250, US20100331599Al), which opens up a new direction for studying the C4 alkylation field. Domestic patents also disclose that the ionic liquid/super acid coupling catalyst adopting the ionic liquid surfactant as the auxiliary agent is used for carrying out isobutane alkylation reaction (CNI01885655A, CNI02134507A, CN101851526A and CN104232153), and the good catalytic effect is also shown, and the addition of the auxiliary agent can obviously prolong the cycle service life of the ionic liquid/super acid fused catalyst. The waste sulfuric acid containing the auxiliary agent contains about 10-15% of acidic grease, auxiliary agent and water, and has brown or black brown appearance and strong pungent odor. The cost of the auxiliary agent is generally higher, the regeneration process of the waste acid commonly used in the industry at present is a high-temperature pyrolysis method, organic matters such as acid soluble oil and the like are burnt at high temperature to produce carbon dioxide and then discharged into the atmosphere, and the auxiliary agent is also decomposed at high temperature.
With the increasingly strict environmental requirements and the pressure on cost, the waste sulfuric acid is a difficult problem troubling production enterprises, and the resource treatment of the alkylated waste acid containing the ionic liquid auxiliary agent is imperative. If the method is executed according to the national environmental protection policy and the easy-to-prepare chemical product management regulations, most domestic enterprises producing waste sulfuric acid need to be shut down. Chemically, waste refers to unused materials, and if these materials are effectively used, not only can pollution be significantly reduced, but also resources can be saved.
Common solid sulfonic acid catalysts comprise sulfamic acid, p-toluenesulfonic acid, sulfonic resin, biomass carbon sulfonic acid and the like, and the catalyst is used as a strong protonic acid catalyst and widely applied to acid catalytic reactions such as esterification, etherification, dehydration, hydration, isomerization and the like. When the p-toluenesulfonic acid and the sulfamic acid are used for catalyzing organic reaction, the p-toluenesulfonic acid and the sulfamic acid are easily dissolved in water to form liquid acid catalysis, and have the defects of difficult separation, strong corrosivity, serious pollution and the like. The sulfonic acid resin has low temperature resistance, and the silicon-based solid sulfonic acid obtained by silanization and oxidation on a silicon-based material has long preparation time and complicated operation. The solid sulfonic acid prepared by carbonizing biomass by sulfuric acid and sulfonating by sulfonating agent has the defects of more preparation procedures, high cost and the like.
The acid soluble oil in the waste acid is a mixture with a wide boiling point, is a highly unsaturated and ionized complex mixture, has wide molecular weight distribution and a complex structure, is mainly sulfate and is a hydrocarbon compound mostly consisting of five C atom rings and branched chains, and has 2-4 double bonds in each molecule on average, wherein two of the double bonds are conjugated double bonds which are probably distributed on the cyclic hydrocarbon and the branched chains thereof respectively. Unsaturated double bonds and hydrogen bonds of the acid-soluble hydrocarbon molecules are utilized to carry out reactions such as esterification, sulfonation, polymerization, carbonization and the like in sulfuric acid, so as to generate the carbon-based acidic material containing sulfonyl, sulfonic acid group, acidic ionic liquid and other groups. Therefore, the regeneration of the waste sulfuric acid can not only greatly reduce the environmental pollution, but also recycle a part of sulfuric acid resources and carbon resources, and has great economic and environmental benefits.
Disclosure of Invention
The invention aims to provide a method for preparing a carbon-based acidic material by using alkylated waste acid containing ionic liquid, and aims to solve the problem of resource utilization of waste sulfuric acid generated by alkylate oil obtained by alkylation synthesis of isobutane and olefin.
The embodiment of the invention is realized by providing a method for preparing a carbon-based acidic material by using alkylated waste acid containing ionic liquid, which comprises the following steps:
and heating the alkylated waste acid containing the ionic liquid auxiliary agent to 100-500 ℃, keeping the temperature for 1-10 hours, washing the product to be neutral by using a solvent, and drying to obtain the carbon-based acidic material, wherein the solvent is at least one of water, dilute sulfuric acid, ammonia water and ammonium sulfate.
The method for preparing the carbon-based acidic material by using the alkylated waste acid containing the ionic liquid utilizes the acid-soluble oil and the ionic liquid in the alkylated waste sulfuric acid to heat and polymerize in the sulfuric acid solution to obtain the carbon-based acidic material containing the ionic liquid, thereby realizing the separation of organic matters and sulfuric acid in the waste acid. The method for preparing the carbon-based acidic material by using the alkylated waste acid containing the ionic liquid has the advantages of short process route, small investment, simple operation, low operation cost and wide application range, can realize resource recycling of organic matters, the ionic liquid and the sulfuric acid in the waste sulfuric acid, reduces carbon emission, and performs resource treatment on the waste sulfuric acid generated by synthesizing the alkylated oil by using the ionic liquid to cooperatively catalyze isobutane and olefin alkylation.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention is realized by providing a method for preparing a carbon-based acidic material by using alkylated waste acid containing ionic liquid, which comprises the following steps:
and heating the alkylated waste acid containing the ionic liquid auxiliary agent to 100-500 ℃, keeping for 1-10 h, washing the product to be neutral by using a solvent, and drying to obtain the carbon-based acidic material, wherein the solvent is at least one of water, ammonia water and ammonium sulfate.
Specifically, organic impurities such as ionic liquid and acid soluble oil in the alkylated waste acid containing the ionic liquid auxiliary agent undergo a polymerization reaction to obtain a black carbon-based acidic material containing sulfuric acid. The carbon-based acidic material or the activated carbon obtained in the last batch can be added in the heating polymerization process to accelerate the polymerization speed, and the sulfur-containing gas discharged in the heating process is discharged after being washed by dilute sulfuric acid and alkali liquor.
The product washing is carried out at room temperature, the washing can be repeated several times, and the washing solution can be reused. Further, the diluted acid solution after water washing can be further concentrated to obtain concentrated sulfuric acid, and the concentrated and separated water can be further used for washing carbon-based acidic materials; the obtained concentrated sulfuric acid can be adjusted by using fuming sulfuric acid or sulfur trioxide to obtain the concentrated sulfuric acid with the concentration of 90-98% for production.
Furthermore, the product after the ammonia water washing solution is an ammonium sulfate solution, which is obtained after concentration, crystallization and separation, and the ammonium sulfate and ammonium sulfate mother liquor, the ammonium sulfate mother liquor and the water obtained by concentration and separation can still be used for washing carbon-based acidic materials or can be used for preparing ammonium sulfate which is directly used for fertilizer and fertilizer.
According to the method for preparing the carbon-based acidic material by using the alkylated waste acid containing the ionic liquid, which is provided by the embodiment of the invention, the acid-soluble oil and the ionic liquid in the alkylated waste sulfuric acid are used for heating polymerization, esterification, carbonization, sulfonation and other reactions in a sulfuric acid solution to generate the carbon-based material. Because the acid-soluble oil content in the waste sulfuric acid is high, the ionic liquid, the acid-soluble oil and the sulfuric acid have strong binding force, and acid-soluble oil compounds such as the ionic liquid, sulfuric acid esters and the like can be polymerized into carbon-based acidic materials in a sulfuric acid solution in the reaction process of the acid-soluble oil, so that the resource utilization of organic matters and the sulfuric acid is realized. The sulfur content of the carbon-based acidic material can be more than 5% without sulfonation treatment, and the carbon-based acidic material contains 0.1-5% of ionic liquid, has strong acidity, and can be used for acid catalysis. The polymerized carbon material can also be obtained by adjusting the polymerization process, and can replace petroleum coke to be used for electrodes and fuel. Meanwhile, the organic matter content of dilute sulfuric acid obtained in the process is very low, COD is lower than 2000mg/L, and colorless concentrated sulfuric acid is obtained by direct concentration or ammonium sulfate is obtained by direct neutralization by ammonia without decolorization and deodorization treatment.
Examples
Example one
Weighing a certain amount of waste acid in a round-bottom flask (250mL), raising the temperature from room temperature to 140 ℃, maintaining for 5 hours, cooling to room temperature, weighing twice the amount of water of the waste acid, adding the water into the round-bottom flask, stirring overnight at room temperature, performing suction filtration to obtain a filtrate (a dilute sulfuric acid solution) and a filter cake (a carbon-based acidic material), collecting the filtrate into a beaker, slowly adding ammonia water (25-28 wt%) under stirring until the solution is neutral, and evaporating the solution to separate out crystals. Washing the filter cake with deionized water until the filter cake is neutral, drying, detecting the sulfur content by element analysis, and detecting the fluorine content by icp. The filtrate was tested for COD and the results are shown in table 1:
TABLE 1
Example two
Weighing a certain amount of waste acid in a round-bottom flask (250mL), raising the temperature from room temperature to 200 ℃, maintaining for 3 hours, cooling to room temperature, weighing twice the amount of water of the waste acid, adding the water into the round-bottom flask, stirring overnight at room temperature, performing suction filtration to obtain a filtrate (a dilute sulfuric acid solution) and a filter cake (a carbon-based acidic material), collecting the filtrate into a beaker, slowly adding ammonia water (25-28 wt%) under stirring until the solution is neutral, and evaporating the solution to separate out crystals. Washing the filter cake with deionized water until the filter cake is neutral, drying, detecting the sulfur content by element analysis, and detecting the fluorine content by icp. The filtrate was tested for COD and the results are shown in table 2:
TABLE 2
EXAMPLE III
Weighing material quantity nAcetic acid：nEthanol＝1:1.2(nAcetic acid＝0.5mol，nEthanol0.6mol), adding into a three-neck flask with a condenser tube, adding carbon-based acidic material mCarbon-based acidic materialTaking reaction liquid after the reaction is finished as a gas chromatograph, wherein the conversion rate of acetic acid is 98.5 percent, and the carbon-based acidic material is prepared at the reaction temperature T of 60 ℃ for 2hThe material has good catalytic activity.
The applicant states that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting, although the present invention is described in detail with reference to the preferred embodiments, those skilled in the art can understand that modifications or equivalent substitutions can be made on the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, which shall be covered by the claims of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (7)
1. A method for preparing a carbon-based acidic material by using alkylated waste acid containing ionic liquid comprises the following steps:
heating the alkylated waste acid containing the ionic liquid auxiliary agent to 100-500 ℃, keeping for 1-10 h, washing the product to be neutral by using a solvent, and drying at 60-200 ℃ to obtain the carbon-based acidic material, wherein the solvent is at least one of water or ammonia water.
2. The method for preparing carbon-based acidic material using alkylated waste acid containing ionic liquid according to claim 1, wherein the sulfur-containing gas discharged during the heating process is discharged after being washed with dilute sulfuric acid and alkali solution.
3. The method for preparing carbon-based acidic material using alkylated waste acid containing ionic liquid according to claim 1, wherein the product washing is performed at room temperature, the washing is repeated several times, and the washing solution can be reused.
4. The method for preparing carbon-based acidic material from alkylated waste acid containing ionic liquid according to claim 1, wherein the drying temperature of the product is 60-200 ℃, the drying pressure is-0.1 MPa, and the drying time is 0.5-5 hours.
5. The method for preparing carbon-based acidic material by using alkylated waste acid containing ionic liquid as claimed in claim 1, wherein the dilute acid solution is further concentrated to obtain concentrated sulfuric acid after washing, and the concentrated and separated water can be further used for washing the carbon-based acidic material.
6. The method for preparing carbon-based acidic material from alkylated waste acid containing ionic liquid as claimed in claim 1, wherein the product obtained after ammonia washing is ammonium sulfate solution, and ammonium sulfate is obtained after concentration, crystallization and separation.
7. The carbon-based acidic material obtained by the method for preparing the carbon-based acidic material by using the alkylated waste acid containing the ionic liquid according to any one of claims 1 to 6, which is used as a catalyst for esterification and etherification reactions.
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| CN108751162B (en) * | 2018-07-05 | 2023-03-21 | 北京中富瑞科环保科技有限公司 | Carbonization treatment method of antibiotic fungi residues |
| CN108910858B (en) * | 2018-07-05 | 2023-04-07 | 北京中富瑞科环保科技有限公司 | Resourceful treatment method for organic medical waste |
| CN110092358A (en) * | 2019-05-24 | 2019-08-06 | 华东理工大学 | A kind of processing method of waste sulfuric acid from alkylation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4014982A (en) * | 1975-06-30 | 1977-03-29 | Texaco Development Corporation | Combined process for upgrading spent alkylation acid and reducing noxious gas content of waste gaseous streams |
| CN87100790A (en) * | 1987-02-18 | 1988-08-31 | 李寿彬 | A kind of treatment process of waste sulfuric acid from alkylation |
| CN104229746A (en) * | 2014-09-18 | 2014-12-24 | 中石化南京工程有限公司 | New method for preparing sulfur from alkylated waste acid |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4014982A (en) * | 1975-06-30 | 1977-03-29 | Texaco Development Corporation | Combined process for upgrading spent alkylation acid and reducing noxious gas content of waste gaseous streams |
| CN87100790A (en) * | 1987-02-18 | 1988-08-31 | 李寿彬 | A kind of treatment process of waste sulfuric acid from alkylation |
| CN104229746A (en) * | 2014-09-18 | 2014-12-24 | 中石化南京工程有限公司 | New method for preparing sulfur from alkylated waste acid |
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