CN104291277A - Environment-friendly production process for producing sulfuric acid by using waste sulfuric acid by virtue of sulfur reduction - Google Patents
Environment-friendly production process for producing sulfuric acid by using waste sulfuric acid by virtue of sulfur reduction Download PDFInfo
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- CN104291277A CN104291277A CN201410502736.9A CN201410502736A CN104291277A CN 104291277 A CN104291277 A CN 104291277A CN 201410502736 A CN201410502736 A CN 201410502736A CN 104291277 A CN104291277 A CN 104291277A
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- sulfuric acid
- sulfur dioxide
- waste sulfuric
- production process
- waste
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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
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
Abstract
The invention relates to an environment-friendly production process for producing sulfuric acid by using waste sulfuric acid by virtue of sulfur reduction. The production process comprises the following steps: firstly concentrating waste sulfuric acid until the content of sulfuric acid is above 80% and then adding sulfur and waste sulfuric acid at a ratio of 1: (5.5-6.5) into a reactor, heating to 200 DEG C-250 DEG C, reducing the sulfuric acid to produce sulfur dioxide, cooling the produced sulfur dioxide by virtue of circulating water in a heat exchanger, removing high-boiling-point impurities and then cooling with cold brine for liquefying sulfur dioxide to remove non-condensable gas, and then vaporizing, liquefied sulfur dioxide, drying sulfur dioxide gas with concentrated sulfur dioxide to remove moisture in sulfur dioxide and then producing sulfuric acid according to the conventional production process, such as catalytic oxidation and absorption. The process and device are simple, the heating temperature is low, the energy consumption is low, the production cost is reduced, the problem of difficulty in processing of waste sulfuric acid is not only solved, and the production process further provides a novel idea for solving the problems of high temperature and high energy consumption of the conventional production process of sulfuric acid and has great innovation and universal applicability for the preparation process of high concentrated sulfuric acid.
Description
Technical field
The present invention relates to a kind of high vitriol oil preparation method, particularly relate to the environment-friendly production process that a kind of sulphur reduction Waste Sulfuric Acid produces sulfuric acid.
Background technology
The present invention relates to a kind of Waste Sulfuric Acid utilization process, belong to field of Environment Protection.
Sulfuric acid is applied to industrial every aspect, while utilization, produce again a large amount of Waste Sulfuric Acids, Waste Sulfuric Acid is a great problem of puzzlement manufacturing enterprise always, if performed in strict accordance with the environmental protection policy of country and regulation on Management of Drug-Making Chemicals, the enterprise of domestic many generation Waste Sulfuric Acids will close down, because the product producing Waste Sulfuric Acid is countless, be applied to all trades and professions of national economy, once stop production, the impact caused is inestimable, and therefore, the recycle of Waste Sulfuric Acid is just aobvious more and more important.
The technique of existing Waste Sulfuric Acid reduction Sulphuric acid, after Waste Sulfuric Acid concentrate, at about 1100 DEG C, with Sweet natural gas Pintsch process reduction Waste Sulfuric Acid, first generate sulfurous gas, sulfurous gas is after series of processes purification, produce sulfuric acid through the operation such as conversion, absorption again, this technique provides thermal source and as reductive agent, reduction temperature is higher using Sweet natural gas, temperature of reaction is at 1000-1100 DEG C, under this condition, equipment anticorrosion is serious, and maintenance cost is high, and often seepage occurs, cause industrial accident, bring very big hidden danger to the production of enterprise, safety.This patent is reductive agent with sulphur, and temperature of reaction is low, and equipment more easily realizes, and solves prior art high to equipment requirements, and energy consumption is high, the problem that production cost is higher.
Summary of the invention
The present invention is for solving the problems of the technologies described above, and the environment-friendly production process providing a kind of sulphur to reduce Waste Sulfuric Acid production sulfuric acid, adopts following technical scheme:
Sulphur reduction Waste Sulfuric Acid produces a method for the environment-friendly production process of sulfuric acid, and the method comprises the steps:
A) Waste Sulfuric Acid not containing or contain a small amount of inorganic salt is concentrated into sulfuric acid concentration expressed in percentage by weight and is greater than 80%, with sulfur reaction at 200 DEG C-250 DEG C, produce sulfur dioxide gas;
B) step a) in the sulfur dioxide gas that produces carry out cooling vaporization, after vitriol oil carrying out washing treatment, obtain pure sulfur dioxide gas;
C) step b) in pure sulfur dioxide gas carry out catalyzed oxidation, obtain sulfur trioxide gas, with water absorb, obtain target product.
Preferably, the reduction temperature 220 DEG C-240 DEG C of step a) described sulphur and Waste Sulfuric Acid.
Preferred, the reduction temperature 210 DEG C of step a) described sulphur and Waste Sulfuric Acid.
Preferably, the weight percent of step a) described sulphur and Waste Sulfuric Acid is 1:5.5-6.5.
Preferably, step a) described Waste Sulfuric Acid obtained by sulfonation or nitration processes.
Preferably, step b) described cooling is treated to interchanger circulating water cooling, cool brine is lowered the temperature or both co-treatments.
Preferably, step b) described sulfurous gas siccative is the vitriol oil.
Beneficial effect of the present invention:
1. the invention provides a kind of sulphur at 200 DEG C-250 DEG C, reduce the technique of Waste Sulfuric Acid, be that reductive agent instead of tradition and provides thermal source and as the fragmentation pattern of reductive agent using Sweet natural gas with sulphur, not only temperature of reaction is low, and avoids equipment corrosion problem, and equipment more easily realizes.The requirement of People's Republic of China's industrial sulphuric acid standard (GB/T 534-2002) acceptable end product is met, product qualification rate reaching more than 98.2% with sulfuric acid prepared by the method.
2. this processing unit is simple, Heating temperature is low, energy consumption is low, production cost is lower, it not only solves the reluctant problem of Waste Sulfuric Acid, the problem more solving traditional sulfuric acid preparation technology high temperature high energy consumption provides new approaches, has great innovative and general applicability to the preparation technology of the high vitriol oil.
3. sulfuric acid can be removed high-boiling-point impurity by the sulfurous gas that sulphur reduction generates after interchanger circulating water cooling, then can remove non-condensable gases through cool brine cooling.
Accompanying drawing explanation
Fig. 1 this programme height vitriol oil preparation flow figure
Embodiment
Mode by the following examples further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, conventionally selects with condition.
Embodiment 1: the Waste Sulfuric Acid producing 2.4-diamino benzene sulfonic acid sodium, content 52%, gets 1000 parts, be concentrated to 80%, remain about 650 parts, be under agitation heated to 210 DEG C, add 84 parts of sulphur, produce sulfurous gas, first through interchanger cooling, icy salt solution cooling liquefaction, then obtain pure sulfurous gas after vaporization, vitriol oil washing, carry out catalyzed oxidation again, obtain sulphur trioxide, absorb with water, obtain 750 parts, 98% sulfuric acid.
Embodiment 2: the Waste Sulfuric Acid producing the amino 3.6.8-naphthalene trisulfonic acid of 2-, content 40%, gets 1000 parts, is concentrated to 80%, remains 500 parts, is under agitation heated to 220 DEG C-240 DEG C, adds 65 parts, sulphur, produces sulfurous gas.First through interchanger cooling, icy salt solution cooling liquefaction, then through vaporization, obtain sulphur trioxide after vitriol oil washing, then generate sulphur trioxide through catalyzed oxidation, absorb with water and obtain 580 parts, 98% sulfuric acid.
Embodiment 3
Carry out quality product detection to the sulfuric acid prepared according to the method in above-described embodiment, target level of product quality performs People's Republic of China's industrial sulphuric acid standard (GB/T 534-2002) acceptable end product specification, and prepared sulfuric acid quality meets following table requirement.
Table 1 sulfuric acid quality index table
By reference to the accompanying drawings the specific embodiment of the present invention is described although above-mentioned; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (7)
1. sulphur reduction Waste Sulfuric Acid produces an environment-friendly production process for sulfuric acid, and it is characterized in that, this technique comprises the steps:
A) Waste Sulfuric Acid not containing or contain a small amount of inorganic salt is concentrated into sulfuric acid concentration expressed in percentage by weight and is greater than 80%, with sulfur reaction at 200 DEG C-250 DEG C, produce sulfur dioxide gas;
B) step a) in the sulfur dioxide gas that produces carry out lowering the temperature, vaporize, vitriol oil carrying out washing treatment, obtain pure sulfur dioxide gas;
C) step b) in pure sulfur dioxide gas through catalyzed oxidation, obtain sulfur trioxide gas, with water absorb, obtain target product.
2. technique according to claim 1, is characterized in that, the reduction temperature 220 DEG C-240 DEG C of step a) described sulphur and Waste Sulfuric Acid.
3. technique according to claim 2, is characterized in that, the reduction temperature 210 DEG C of step a) described sulphur and Waste Sulfuric Acid.
4. technique according to claim 1, is characterized in that, the weight percent of step a) described sulphur and Waste Sulfuric Acid is 1:5.5-6.5.
5. technique according to claim 1, it is characterized in that, step a) described Waste Sulfuric Acid is obtained by sulfonation or nitration processes.
6. technique according to claim 1, is characterized in that, step b) described cooling is treated to interchanger circulating water cooling, cool brine cooling or both co-treatments.
7. technique according to claim 1, is characterized in that, step b) described sulfurous gas siccative is the vitriol oil.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410502736.9A CN104291277A (en) | 2014-09-26 | 2014-09-26 | Environment-friendly production process for producing sulfuric acid by using waste sulfuric acid by virtue of sulfur reduction |
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| CN201410502736.9A CN104291277A (en) | 2014-09-26 | 2014-09-26 | Environment-friendly production process for producing sulfuric acid by using waste sulfuric acid by virtue of sulfur reduction |
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| CN201410502736.9A Pending CN104291277A (en) | 2014-09-26 | 2014-09-26 | Environment-friendly production process for producing sulfuric acid by using waste sulfuric acid by virtue of sulfur reduction |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673017A (en) * | 2017-02-17 | 2017-05-17 | 四川省中明环境治理有限公司 | Environment-friendly production method for preparing sodium sulfite by utilizing sulfur to reduce waste sulfuric acid |
| CN106748900A (en) * | 2017-02-17 | 2017-05-31 | 四川省中明环境治理有限公司 | A kind of Waste Sulfuric Acid prepares the environment-protection production method of paratoluenesulfonic acid sodium salt |
| CN109052335A (en) * | 2018-07-24 | 2018-12-21 | 上海三夫工程技术有限公司 | A kind of method of sulfur gas reduction Waste Sulfuric Acid sulfur dioxide liquid and sulfuric acid |
| CN109364723A (en) * | 2018-11-07 | 2019-02-22 | 江西理工大学 | A kind of method that sulfur trioxide is reduced to sulfur dioxide in Flue Gas of Nonferrous Smelting |
| CN115821065A (en) * | 2022-12-21 | 2023-03-21 | 黑龙江紫金铜业有限公司 | Recycling method for recycling arsenic and leaching residues from black copper mud and arsenic filter cake |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2389071A (en) * | 1943-04-07 | 1945-11-13 | Gen Chemical Corp | Production of sulphur dioxide |
| US4053573A (en) * | 1975-11-20 | 1977-10-11 | Allied Chemical Corporation | Recovery of sulfur values from spent sulfuric acid |
| CN101200288A (en) * | 2006-09-08 | 2008-06-18 | 催化剂蒸馏技术公司 | Low temperature process for regenerating spent sulfuric acid |
| CN103569972A (en) * | 2013-11-12 | 2014-02-12 | 广西科技大学 | Preparation method of sulfur dioxide gas in sugar industry |
| CN103626135A (en) * | 2013-12-04 | 2014-03-12 | 山东凯盛新材料股份有限公司 | Method and equipment for producing liquid sulfur dioxide through sulfur trioxide and sulphur |
-
2014
- 2014-09-26 CN CN201410502736.9A patent/CN104291277A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2389071A (en) * | 1943-04-07 | 1945-11-13 | Gen Chemical Corp | Production of sulphur dioxide |
| US4053573A (en) * | 1975-11-20 | 1977-10-11 | Allied Chemical Corporation | Recovery of sulfur values from spent sulfuric acid |
| CN101200288A (en) * | 2006-09-08 | 2008-06-18 | 催化剂蒸馏技术公司 | Low temperature process for regenerating spent sulfuric acid |
| CN103569972A (en) * | 2013-11-12 | 2014-02-12 | 广西科技大学 | Preparation method of sulfur dioxide gas in sugar industry |
| CN103626135A (en) * | 2013-12-04 | 2014-03-12 | 山东凯盛新材料股份有限公司 | Method and equipment for producing liquid sulfur dioxide through sulfur trioxide and sulphur |
Non-Patent Citations (1)
| Title |
|---|
| F. RUSSELL BICHOWSKY: "EQUILIBRIUM IN THE REACTION BETWEEN SULFUR DIOXIDE", 《JOURNAL OF AMERICAN CHEMICAL SOCIETY》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673017A (en) * | 2017-02-17 | 2017-05-17 | 四川省中明环境治理有限公司 | Environment-friendly production method for preparing sodium sulfite by utilizing sulfur to reduce waste sulfuric acid |
| CN106748900A (en) * | 2017-02-17 | 2017-05-31 | 四川省中明环境治理有限公司 | A kind of Waste Sulfuric Acid prepares the environment-protection production method of paratoluenesulfonic acid sodium salt |
| CN106748900B (en) * | 2017-02-17 | 2018-10-23 | 四川省中明环境治理有限公司 | A kind of Waste Sulfuric Acid prepares the environment-protection production method of paratoluenesulfonic acid sodium salt |
| CN109052335A (en) * | 2018-07-24 | 2018-12-21 | 上海三夫工程技术有限公司 | A kind of method of sulfur gas reduction Waste Sulfuric Acid sulfur dioxide liquid and sulfuric acid |
| CN109052335B (en) * | 2018-07-24 | 2023-08-22 | 上海三夫工程技术有限公司 | Method for preparing liquid sulfur dioxide and sulfuric acid by reducing waste sulfuric acid with sulfur gas |
| CN109364723A (en) * | 2018-11-07 | 2019-02-22 | 江西理工大学 | A kind of method that sulfur trioxide is reduced to sulfur dioxide in Flue Gas of Nonferrous Smelting |
| CN109364723B (en) * | 2018-11-07 | 2021-05-11 | 江西理工大学 | Method for reducing sulfur trioxide in non-ferrous smelting flue gas into sulfur dioxide |
| CN115821065A (en) * | 2022-12-21 | 2023-03-21 | 黑龙江紫金铜业有限公司 | Recycling method for recycling arsenic and leaching residues from black copper mud and arsenic filter cake |
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