CN105923615B - A kind of nitrating wasting acid recycling prepares the production technology of nitrosyl sulfuric acid - Google Patents
A kind of nitrating wasting acid recycling prepares the production technology of nitrosyl sulfuric acid Download PDFInfo
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- CN105923615B CN105923615B CN201610283726.XA CN201610283726A CN105923615B CN 105923615 B CN105923615 B CN 105923615B CN 201610283726 A CN201610283726 A CN 201610283726A CN 105923615 B CN105923615 B CN 105923615B
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- nitrating wasting
- nitrosyl sulfuric
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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
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
- C01B21/093—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more sulfur atoms
- C01B21/094—Nitrosyl containing acids
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the production technologies that a kind of nitrating wasting acid recycling prepares nitrosyl sulfuric acid, nitrating wasting acid and extractant are mixed first, it extracts under certain condition, then organic solvent is recycled into extraction phase rectifying, raffinate phase is sent into reaction tower, and sulfur dioxide and nitric acid are added into reaction tower, and reaction to liquid is in blue, reaction terminates, and obtains nitrosyl sulfuric acid.The preparation method is simple, using nitrating wasting acid as raw material, greatly reduces production cost, nitrosyl sulfuric acid high income.
Description
Technical field：
The present invention relates to organic chemical industry's nitration reaction technical field, it is specifically related to a kind of nitrating wasting acid recycling and prepares nitrous
The production technology of acyl sulfate.
Background technology：
Nitration reaction is common organic reaction, is by Organic Ingredients temperature reaction in the nitration mixture that sulfuric acid, nitric acid are prepared
Prepare the reaction of organic matter.To improve conversion ratio of the organic matter in nitration reaction, the molal quantity of nitric acid is higher than in usual nitration mixture
The theoretical value of nitric acid needed for nitrification completely occurs for organic matter.After the completion of nitration reaction, by organic phase separation, excessive nitric acid residual
In sulfuric acid, that is, form nitrating wasting acid.
Nitrating wasting acid is a kind of strong corrosive and reluctant industrial waste, also there is dissolving part nitration product in spent acid
And unreacted raw material, while being also a kind of potential Sulphur ressource, as domestic Sulphur ressource is in short supply increasingly tight with environmental requirement
Lattice carry out recycling to nitrating wasting acid, are the necessary conditions for realizing sustainable development.
Diazotising is the important reaction member of organic synthesis, and sodium nitrite is common diazo-reaction raw material.Work as phenyl ring
On have other groups in the presence of, the activity of amino reduces, and at this moment needs the higher diazotising raw material nitrosyl sulfuric acid of activity.With Asia
Sodium nitrate is compared, and sodium sulfate salt will not be generated when nitrosyl sulfuric acid is reacted as diazotization agent, convenient for dilute sulfuric acid in subsequent handling
Concentration and recovery.The nitrosyl sulfuric acid solution generated using sodium nitrite method, since the niter cake of reaction generation is in sulfuric acid
Solubility it is smaller, often formed crystallization, make material retrogradation, be unfavorable for reacting.And the nitrous for using sulfur dioxide method to generate
Acyl sulfate solution can less plus sulfuric acid due to the generation of not no niter cake, and production cost and yield all greatly improve.
Invention content：
The object of the present invention is to provide the production technology that a kind of nitrating wasting acid recycling prepares nitrosyl sulfuric acid, the process conditions
Mildly, the yield of nitrosyl sulfuric acid is high, and production cost is low.
To achieve the above object, the present invention uses following technical scheme：
A kind of nitrating wasting acid recycling prepares the production technology of nitrosyl sulfuric acid, includes the following steps：
(1) nitrating wasting acid and extractant are uniformly mixed in extraction tower, isolated extraction phase recycles molten after rectifying
Agent；
(2) isolated raffinate phase is delivered in reaction tower, and nitric acid and sulfur dioxide is added into reaction tower, instead
When should become au bleu to the color of liquid in reaction tower, reaction terminating is to get to nitrosyl sulfuric acid.
As a preferred embodiment of the above technical solution, the nitrating wasting acid is the spent acid that manufacturing process is nitrified from any phenyl ring.
As a preferred embodiment of the above technical solution, in step (1), the extractant is dichloromethane, chloroform, two chloroethenes
One or more mixing in alkane.
As a preferred embodiment of the above technical solution, in step (1), the temperature of the extraction is 40-75 DEG C.
As a preferred embodiment of the above technical solution, in step (2), the mass ratio of the nitrating wasting acid and extractant is 5-8：1.
As a preferred embodiment of the above technical solution, in step (2), the mass ratio of the nitric acid, sulfur dioxide and raffinate phase is
4：1-3：7.
As a preferred embodiment of the above technical solution, in step (2), reaction is controlled by controlling the addition speed of sulfur dioxide
Temperature be 60-65 DEG C.
As a preferred embodiment of the above technical solution, the water content of the raffinate phase is less than 10%.
The invention has the advantages that：
The present invention prepares nitrosyl sulfuric acid using nitrating wasting acid, solves pollution problem of the nitrating wasting acid to environment, cuts
The present invention substantially increases solvent by reasonably selecting the type of extractant and the amount ratio of extractant and nitrating wasting acid
The rate of recovery；
On the other hand, the present invention rationally adjusts the dosage of raffinate phase and nitric acid, sulfur dioxide, and by controlling sulfur dioxide
Addition speed, the temperature to control reaction is 60-65 DEG C so that the yield for the nitrosyl sulfuric acid being prepared is up to 75%~
99%.
Description of the drawings：
Fig. 1 is the production procedure schematic diagram that nitrating wasting acid recycling prepares nitrosyl sulfuric acid.
Specific implementation mode：
In order to better understand the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving
The present invention is released, any restriction will not be constituted to the present invention：
Embodiment 1
A kind of nitrating wasting acid recycling prepares the production technology of nitrosyl sulfuric acid, includes the following steps：
(1) 500g nitrating wasting acids and 100g dichloromethane are uniformly mixed in extraction tower, are extracted at 40 DEG C, it is isolated
Extraction phase after rectifying recycling design；
(2) isolated raffinate phase is delivered in reaction tower, and nitric acid and sulfur dioxide is added into reaction tower, control
The addition speed of sulfur dioxide processed is 60-65 DEG C come the temperature for controlling reaction, reacts to the color of liquid in reaction tower and becomes blue
When color, for reaction terminating to get to nitrosyl sulfuric acid, the wherein mass ratio of nitric acid, sulfur dioxide and raffinate phase is 4：1：7, nitrous
The yield of acyl sulfate is 75%.
Embodiment 2
A kind of nitrating wasting acid recycling prepares the production technology of nitrosyl sulfuric acid, includes the following steps：
(1) 800g nitrating wasting acids and 100g dichloromethane are uniformly mixed in extraction tower, are extracted at 75 DEG C, it is isolated
Extraction phase after rectifying recycling design；
(2) isolated raffinate phase is delivered in reaction tower, and nitric acid and sulfur dioxide is added into reaction tower, control
The addition speed of sulfur dioxide processed is 60-65 DEG C come the temperature for controlling reaction, reacts to the color of liquid in reaction tower and becomes blue
When color, for reaction terminating to get to nitrosyl sulfuric acid, the wherein mass ratio of nitric acid, sulfur dioxide and raffinate phase is 4：3：7, nitrous
The yield of acyl sulfate is 75%.
Embodiment 3
A kind of nitrating wasting acid recycling prepares the production technology of nitrosyl sulfuric acid, includes the following steps：
(1) mixture of 600g nitrating wasting acids and 100g dichloromethane, chloroform, dichloroethanes is mixed in extraction tower
Uniformly, it is extracted at 50 DEG C, isolated extraction phase recycling design after rectifying；
(2) isolated raffinate phase is delivered in reaction tower, and nitric acid and sulfur dioxide is added into reaction tower, control
The addition speed of sulfur dioxide processed is 60-65 DEG C come the temperature for controlling reaction, reacts to the color of liquid in reaction tower and becomes blue
When color, for reaction terminating to get to nitrosyl sulfuric acid, the wherein mass ratio of nitric acid, sulfur dioxide and raffinate phase is 4：1.5：7, it is sub-
The yield of nitryl sulfuric acid is 80%.
Embodiment 4
A kind of nitrating wasting acid recycling prepares the production technology of nitrosyl sulfuric acid, includes the following steps：
(1) 650g nitrating wasting acids and 100g dichloromethane are uniformly mixed in extraction tower, are extracted at 55 DEG C, it is isolated
Extraction phase after rectifying recycling design；
(2) isolated raffinate phase is delivered in reaction tower, and nitric acid and sulfur dioxide is added into reaction tower, control
The addition speed of sulfur dioxide processed is 60-65 DEG C come the temperature for controlling reaction, reacts to the color of liquid in reaction tower and becomes blue
When color, for reaction terminating to get to nitrosyl sulfuric acid, the wherein mass ratio of nitric acid, sulfur dioxide and raffinate phase is 4：2：7, nitrous
The yield of acyl sulfate is 85%.
Embodiment 5
A kind of nitrating wasting acid recycling prepares the production technology of nitrosyl sulfuric acid, includes the following steps：
(1) 700g nitrating wasting acids and 100g dichloromethane are uniformly mixed in extraction tower, are extracted at 60 DEG C, it is isolated
Extraction phase after rectifying recycling design；
(2) isolated raffinate phase is delivered in reaction tower, and nitric acid and sulfur dioxide is added into reaction tower, control
The addition speed of sulfur dioxide processed is 60-65 DEG C come the temperature for controlling reaction, reacts to the color of liquid in reaction tower and becomes blue
When color, for reaction terminating to get to nitrosyl sulfuric acid, the wherein mass ratio of nitric acid, sulfur dioxide and raffinate phase is 4：2.5：7, it is sub-
The yield of nitryl sulfuric acid is 85%.
Embodiment 6
A kind of nitrating wasting acid recycling prepares the production technology of nitrosyl sulfuric acid, includes the following steps：
(1) 750g nitrating wasting acids and 100g dichloromethane are uniformly mixed in extraction tower, are extracted at 50 DEG C, it is isolated
Extraction phase after rectifying recycling design；
(2) isolated raffinate phase is delivered in reaction tower, and nitric acid and sulfur dioxide is added into reaction tower, control
The addition speed of sulfur dioxide processed is 60-65 DEG C come the temperature for controlling reaction, reacts to the color of liquid in reaction tower and becomes blue
When color, for reaction terminating to get to nitrosyl sulfuric acid, the wherein mass ratio of nitric acid, sulfur dioxide and raffinate phase is 4：1.8：7, it is sub-
The yield of nitryl sulfuric acid is 99%.
Claims (4)
1. a kind of nitrating wasting acid recycling prepares the production technology of nitrosyl sulfuric acid, which is characterized in that include the following steps：
(1) nitrating wasting acid and extractant are uniformly mixed in extraction tower, isolated extraction phase recycling design after rectifying；Its
In, the nitrating wasting acid is the spent acid that manufacturing process is nitrified from any phenyl ring；The temperature of extraction is 40-75 DEG C；Nitrating wasting acid
Mass ratio with extractant is 5-8：1；
(2) isolated raffinate phase is delivered in reaction tower, and nitric acid and sulfur dioxide is added into reaction tower, reaction is extremely
When the color of liquid becomes au bleu in reaction tower, reaction terminating is to get to nitrosyl sulfuric acid；Wherein, nitric acid, sulfur dioxide and extraction
The mass ratio of remaining phase is 4：1-3：7.
2. a kind of nitrating wasting acid recycling as described in claim 1 prepares the production technology of nitrosyl sulfuric acid, which is characterized in that step
Suddenly in (1), the extractant is one or more mixing of dichloromethane, chloroform, dichloroethanes.
3. a kind of nitrating wasting acid recycling as described in claim 1 prepares the production technology of nitrosyl sulfuric acid, which is characterized in that step
Suddenly it is 60-65 DEG C by the temperature for controlling the addition speed of sulfur dioxide to control reaction in (2).
4. a kind of nitrating wasting acid recycling as described in claim 1 prepares the production technology of nitrosyl sulfuric acid, which is characterized in that institute
The water content for stating raffinate phase is less than 10%.
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| CN107963617B (en) * | 2017-12-28 | 2019-11-01 | 浙江迪邦化工有限公司 | A kind of production method and system of nitrosyl sulfuric acid |
| CN109485025A (en) * | 2018-12-10 | 2019-03-19 | 杭州申航新材料有限公司 | The continuous production device and method of nitrosyl sulfuric acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4128623A (en) * | 1977-02-15 | 1978-12-05 | Basf Aktiengesellschaft | Manufacture of a solution of nitrosylsulfuric acid in sulfuric acid |
| CN105417509A (en) * | 2015-11-30 | 2016-03-23 | 浙江林江化工股份有限公司 | Preparation method of nitrosyl sulfuric acid and method for separating sulfuric acid and phosphoric acid in industrial waste acid |
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2016
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4128623A (en) * | 1977-02-15 | 1978-12-05 | Basf Aktiengesellschaft | Manufacture of a solution of nitrosylsulfuric acid in sulfuric acid |
| CN105417509A (en) * | 2015-11-30 | 2016-03-23 | 浙江林江化工股份有限公司 | Preparation method of nitrosyl sulfuric acid and method for separating sulfuric acid and phosphoric acid in industrial waste acid |
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Denomination of invention: A production process for recovering nitrifying waste acid to prepare nitrosyl sulfuric acid Effective date of registration: 20230823 Granted publication date: 20180717 Pledgee: Bank of Ningbo Co.,Ltd. Shaoxing Branch Pledgor: ZHEJIANG XIESHI NEW MATERIALS Co.,Ltd. Registration number: Y2023980053412 |
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