CN1279147C - Multistage desulfurizing method for synthetic ammonia system - Google Patents
Multistage desulfurizing method for synthetic ammonia system Download PDFInfo
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- CN1279147C CN1279147C CN 03119053 CN03119053A CN1279147C CN 1279147 C CN1279147 C CN 1279147C CN 03119053 CN03119053 CN 03119053 CN 03119053 A CN03119053 A CN 03119053A CN 1279147 C CN1279147 C CN 1279147C
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Abstract
The present invention discloses a multistage desulfurizing method for a synthetic ammonia system, which relates to semi-water gas desulfurizing technology. After semi-water gas is supplied to a first grade desulfurizing tower to be desulphurized, the semi-water gas is inputted into a second grade desulfurizing tower to be secondarily desulphurized after the semi-water gas is decoked and cooled. The semi-water gas is circularly desulfurized in a multistage mode until a sulfur content is lower than or equal to 0.075 mg/L. The semi-water gas is sent to the next working section after purification, cleaning, impurity removing and pressurization. The sulfur content of outlet gas can be effectively lowered, and the blocking of the desulfurizing towers is prevented. The corrosion of equipment is relieved, production cost is lowered, and environmental pollution is reduced.
Description
Technical Field
The invention relates to a desulfurization method applied to an ammonia synthesis system, which is mainly used for removing sulfur-containing impurities such as hydrogen sulfide and the like in semi-water gas, in particular to a multi-stage desulfurization method of the ammonia synthesis system.
Background
The existing desulfurization method of the ammonia synthesis system is that semi-water gas prepared by the reaction of coal, air and steam is desulfurized once through a first-stage desulfurization tower and then directly enters the next working section, although most of hydrogen sulfide in the semi-water gas is removed, the sulfur content is still maintained to be over 0.15mg/L, the sulfur content of outlet gas is higher, the activity of a catalyst is reduced, the production environment toxicity is higher, the pollution is serious, the corrosion to instruments and equipment in the next working section is serious, the desulfurization tower is easy to block, and the semi-water gas with higher sulfur content causes copper liquid to generate sulfide colloid, so that the copper washing working section cannot normally operate, the production cost of ammonia synthesis is increased, and the serious environment pollution is caused.
Disclosure of Invention
The invention aims to overcome the defects and provide a multistage desulfurization method for a synthetic ammonia system, which removes sulfur-containing impurities in semi-water gas by multistage desulfurization in a preorder section of synthetic ammonia, effectively reduces the sulfur content of outlet gas, prevents a desulfurization tower from being blocked, reduces equipment corrosion, reduces production cost and reduces environmental pollution.
The purpose of the invention is realized as follows: a multi-stage desulfurizing process for the synthetic ammonia system includes such steps as reaction of coal with air and steam to obtain semi-water gas at 40-50 deg.C, 2MPa and 1.5-2.0mg/L of S, alkali washing to remove hydrogen sulfide to the content of S not higher than 0.15mg/L, high-voltage electrostatic removing of coal tar from the bottom of electrostatic decoking tower, delivering it to cooling tower, pressurizing, removing impurities, cooling, reaction with desulfurizing agent to remove hydrogen sulfide to the content of S not higher than 0.075mg/L, purifying, cooling, washing to remove impurities, pressurizing, adding Na to the first desulfurizing tower at 8g/L, and adding Na to the first desulfurizing tower2CO3As a desulfurizer, tannin extract is added into the secondary desulfurizing tower according to the proportion of 1.2g/l to serve as the desulfurizer. And rich liquor formed after the desulfurizer in the first-stage desulfurizing tower and the second-stage desulfurizing tower absorbs hydrogen sulfide enters a rich liquor tank and is pumped into a jet regeneration tank by a rich liquor pump, the desulfurizer is oxidized and floats out of sulfur foam to be regenerated into lean liquor, the lean liquor enters a lean liquor tank and is pumped into the two-stage desulfurizing tower by a lean liquor pump to be recycled, and the sulfur foam enters a foam tank and passes through a sulfur melting kettle to produce sulfur.
The working principle of the desulfurization method is as follows: 1. h in semi-water gas2The S gas is acidic, is input into a desulfurizing tower and is firstly absorbed by alkaline solution to generate NaHS, and the chemical reaction formula is as follows: (ii) a 2. NaHS in solution is replaced by sodium metavanadate NaVO3Oxidizing to generate sodium pyrovanadate Na2V4O9And precipitating S, wherein the chemical reaction formula is as follows: ；3. adding sodium pyrovanadate Na into oxidation state tannin extract TEoS in a desulfurizing tower2V4O9Oxidized into sodium metavanadate NaVO3And simultaneously generating reduced tannin extract TErS by the oxidation state tannin extract TEoS, wherein the chemical reaction formula is as follows: (ii) a 4. The S-rich reduction state tannin extract enters a jet regeneration tank, sulfur foam is floated out after air oxidation to generate oxidation state tannin extract for recycling, and the chemical reaction formula is as follows: 。
according to the desulfurization method, the semi-water gas is subjected to multi-stage desulfurization more than two stages, so that the sulfur content of raw material gas for synthesizing ammonia is effectively reduced, the sulfur content of outlet gas is greatly reduced, the toxicity of the production environment is reduced, instruments and equipment cannot be corroded, meanwhile, the desulfurized semi-water gas enters a copper washing section, so that the influence on normal production caused by sulfide colloid produced by copper liquid is avoided, and the environmental pollution is reduced; the desulfurizer absorbing hydrogen sulfide is oxidized by air and then floats out sulfur foam to be regenerated into barren solution which can be returned to the desulfurizing tower for recycling, so that the production cost is saved; the cooling water entering the cooling cleaning tower exchanges with the semi-water gas and is discharged to a hot water tank, steam can be produced after purification treatment, energy is saved, and the desulfurizer is respectively added into the two stages of desulfurizing towers, so thatthe desulfurizing towers can be effectively prevented from being blocked, and the desulfurizing reaction is sufficient.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1:
reacting coal with air and steam to obtain semi-water gas with sulfur content of 2.0mg/L, pressurizing to 40 deg.C and 2MPa, introducing into a first-stage desulfurizing tower via an input pipeline, and adding Na via a liquid inlet of the first-stage desulfurizing tower at a ratio of 8g/L2CO3And a proper amount of NaVO3As a desulfurizer, the semi-water gas and the desulfurizer are fully reacted, washed by alkali and desulfurized until the sulfur content is 0.15mg/L, then the semi-water gas after the first-stage desulfurization is input to the bottom of an electrostatic decoking tower through an input pipeline, the semi-water gas is output from the upper part after the coal tar is removed by high-voltage static electricity, the semi-water gas is pressurized and then is conveyed to a cooling tower to remove impurities and cool, then the semi-water gas is input to a second-stage desulfurization tower, meanwhile, oxidation state tannin extract TEoS is added into the second-stage desulfurization tower according to the proportion of2CO3、NaVO3As a desulfurizer, the semi-water gas after primary desulfurization fully reacts with the desulfurizer, wherein H2S is removed in a large amount, the sulfur content reaches 0.075mg/L, and H is absorbed by a desulfurizing agent2And S, generating a rich solution, entering the rich solution tank for staying for 5 minutes, pumping the rich solution into a jet regeneration tank by a rich solution pump, oxidizing the reduced-state tannin extract by air to generate oxidized-state tannin extract, floating out sulfur foam, regenerating the rich solution into a lean solution, entering the lean solution tank by a liquid level regulator, pumping the lean solution into a secondary desulfurization tower by a lean solution pump, and recycling. And the semi-water gas after the secondary desulfurization is input into a cooling and cleaning tower through an input pipeline, cooling water enters the upper part of the cooling and cleaning tower to be in countercurrent contact with the desulfurized semi-water gas, impurities are cleaned, the cooling water flows to the lower part of the cooling and cleaning tower through a U-shaped water seal valve to perform heat exchange with the semi-water gas so as to be cooled to 35 ℃, the cooling water is discharged to a hot water tank through a safety water seal at the bottom of the cooling and cleaning tower, and the cooled and cleaned semi-water gas is pressurized and then sent to the next working section.
Example 2:
reacting coal with air and steam to obtain semi-water gas with sulfur content of 1.8mg/L, pressurizing to 35 deg.C and 1.8MPa, introducing into a first-stage desulfurizing tower via an input pipeline, and adding liquid via the first-stage desulfurizing towerAdding Na according to the proportion of 8g/L2CO3And a proper amount of NaVO3As a desulfurizer, the semi-water gas and the desulfurizer are fully reacted, washed by alkali and desulfurized until the sulfur content is 0.10mg/L, then the semi-water gas after the first-stage desulfurization is input to the bottom of an electrostatic decoking tower through an input pipeline, the semi-water gas is output from the upper part after the coal tar is removed by high-voltage static electricity, the semi-water gas is pressurized and then is conveyed to a cooling tower to remove impurities and cool, then the semi-water gas is input to a second-stage desulfurization tower, meanwhile, oxidation state tannin extract TEoS is added into the second-stage desulfurization tower according to the proportion of2CO3、NaVO3As a desulfurizer, the semi-water gas after primary desulfurization fully reacts with the desulfurizer, wherein H2S is removed in a large amount, the sulfur content reaches 0.070mg/L, and H is absorbed by a desulfurizing agent2And S, generating a rich solution, entering a rich solution tank, staying for 3 minutes, pumping the rich solution into a jet regeneration tank by a rich solution pump, oxidizing the reduced tannin extract by air to generate oxidized tannin extract, floating out sulfur foam, regenerating the rich solution into a lean solution, entering the lean solution tank by a liquid level regulator, pumping the lean solution into a secondary desulfurization tower by a lean solution pump, and recycling. And the semi-water gas after the secondary desulfurization is input into a cooling and cleaning tower through an input pipeline, cooling water enters the upper part of the cooling and cleaning tower to be in countercurrent contact with the desulfurized semi-water gas, impurities are cleaned, the cooling water flows to the lower part of the cooling and cleaning tower through a U-shaped water seal valve to perform heat exchange with the semi-water gas so as to be cooled to 40 ℃, the cooling water is discharged to a hot water tank through a safety water seal at the bottom of the cooling and cleaning tower, and the cooled and cleaned semi-water gas is pressurized and then sent to the next working section.
Claims (2)
1. A multi-stage desulfurizing method for ammonia synthesizing system includes the steps of reacting coal with air and steam to prepare semi-water gas with temperature of 40-50 deg.C, pressure of 2MPa and sulfur content of 1.5-2.0mg/L, and is characterized by that: introducing the semi-water gas into a first-stage desulfurizing tower for alkaline washing to remove hydrogen sulfide until the sulfur content is not higher than 0.15mg/L, and then introducing the semi-water gas into the bottom of an electrostatic decoking towerRemoving coal tar by high-voltage static electricity, outputting from the upper part, pressurizing, conveying to a cooling tower to remove impurities and cool, inputting into a secondary desulfurizing tower to react with a desulfurizing agent to remove hydrogen sulfide until the sulfur content is not higher than 0.075mg/L, purifying, inputting into a cooling cleaning tower to cool and clean to further remove impurities, pressurizing, and sending into the next working section for use, wherein Na is added into a primary desulfurizing tower according to the proportion of 8g/L2CO3And a proper amount of NaVO3As a desulfurizer, tannin extract and a proper amount of Na are added into a secondary desulfurizing tower according to the proportion of 1.2g/l2CO3、NaVO3As a desulfurizing agent.
2. The method for multi-stage desulfurization in ammonia synthesis system according to claim 1, wherein: and rich liquor formed after the desulfurizer in the first-stage desulfurizing tower and the second-stage desulfurizing tower absorbs hydrogen sulfide enters a rich liquor tank and is pumped into a jet regeneration tank by a rich liquor pump, the desulfurizer is oxidized and floats out of sulfur foam to be regenerated into lean liquor, the lean liquor enters a lean liquor tank and is pumped into the two-stage desulfurizing tower by a lean liquor pump to be recycled, and the sulfur foam enters a foam tank and passes through a sulfur melting kettle to produce sulfur.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03119053 CN1279147C (en) | 2003-05-09 | 2003-05-09 | Multistage desulfurizing method for synthetic ammonia system |
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| CN 03119053 CN1279147C (en) | 2003-05-09 | 2003-05-09 | Multistage desulfurizing method for synthetic ammonia system |
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| CN1456639A CN1456639A (en) | 2003-11-19 |
| CN1279147C true CN1279147C (en) | 2006-10-11 |
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| CN103285722B (en) * | 2013-06-06 | 2015-01-07 | 浙江晋巨化工有限公司 | Highly sulfur-containing pressurized shifted gas wet-process desulphurization technique |
| CN104910970A (en) * | 2015-05-22 | 2015-09-16 | 张玲 | Series-process coal gas desulfurization process method and desulfurization device therefor |
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Assignee: HUBEI DAJIANG CHEMICAL GROUP Co.,Ltd. Assignor: Hubei Yihua Chemical Industry Co.,Ltd. Contract fulfillment period: 2007.2.14 to 2017.2.13 Contract record no.: 2009420000018 Denomination of invention: Multistage desulfurizing method for synthetic ammonia system Granted publication date: 20061011 License type: Exclusive license Record date: 20090506 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.2.14 TO 2017.2.13; CHANGE OF CONTRACT Name of requester: HUBEI DAJIANG CHEMICAL GROUP CO.,LTD. Effective date: 20090506 |
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Assignee: HUBEI DAJIANG CHEMICAL GROUP Co.,Ltd. Assignor: Hubei Yihua Chemical Industry Co.,Ltd. Contract record no.: 2009420000018 Date of cancellation: 20110725 |
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