CN110964575A - Energy-saving environment-friendly novel synthetic ammonia desulfurization process - Google Patents
Energy-saving environment-friendly novel synthetic ammonia desulfurization process Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1481—Removing sulfur dioxide or sulfur trioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/464—Sulfates of Ca from gases containing sulfur oxides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/061—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases with supplementary heating
- F23G7/065—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases with supplementary heating using gaseous or liquid fuel
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
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Abstract
The invention discloses a new energy-saving and environment-friendly synthetic ammonia desulfurization process, which comprises the steps of treating a feed gas by a sulfur-tolerant shift system, a PSA pressure swing adsorption desulfurization and decarbonization system, a gas-making three-waste gas mixed combustion furnace and a tail gas environment-friendly treatment system in sequence to obtain a calcium sulfate product for sale, thereby achieving the purpose of desulfurization; the invention optimizes the traditional desulfurization process, recycles the combustible effective gas lost by pressure swing adsorption decarburization to generate heat, fundamentally stops the emission of toxic and harmful substances, simultaneously recycles waste heat, saves energy, reduces consumption, greatly improves the scientificity and rationality of the production process and achieves the purposes of energy conservation and environmental protection.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a novel energy-saving and environment-friendly synthetic ammonia desulfurization process.
Background
Small nitrogen fertilizer enterprises in China still account for a large proportion in the nitrogen fertilizer industry until now, and in all the small nitrogen fertilizer enterprises in China running at present, a nitrogen-hydrogen compressor is almost adopted for gas compression. Compared with other types of compressors, the nitrogen-hydrogen compressor has the advantages of minimum investment, the most mature technology and normal operation, thereby occupying huge proportion in small nitrogen fertilizer enterprises in China. However, as the requirement of the country for safe production is strengthened day by day, the problem of manual adjustment of the loop becomes a bottleneck restricting the safe development of the industry. Gaseous compression of china's small nitrogenous fertilizer trade belongs to class A device, and the installation regulation requirement must reach unmanned on duty state, and some small nitrogenous fertilizer enterprises can't normally operate because of the safety problem, and some enterprises face even the nightmare that stops production and remain standstill.
The desulfurization technology commonly adopted in the industry at present comprises two processes of semi-water gas wet desulfurization and conversion gas wet desulfurization, and the desulfurization liquid is pumped into the upper part of a desulfurization tower of a wet desulfurization system through a desulfurization pump, and is in countercurrent contact with feed gas entering from the lower part of the desulfurization tower, so that hydrogen sulfide in the feed gas is removed, the desulfurization liquid is discharged from the lower part of the desulfurization tower and then is pumped into a desulfurization liquid regeneration system through a regeneration pump, the desulfurization liquid is sprayed and regenerated, the hydrogen sulfide in the desulfurization liquid is oxidized to generate elemental sulfur which is suspended on the surface of the desulfurization liquid, and the elemental sulfur is further treated after being filtered into sulfur paste through a filter press regularly. The secondary pollution to the environment caused by the filter pressing and further processing process of the sulfur paste is also the root cause for limiting wet desulphurization and advocating novel coal gasification Claus Tou flow which are proposed for a plurality of times in recent countries and places.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a novel energy-saving and environment-friendly synthetic ammonia desulfurization process, which optimizes the traditional desulfurization process, recycles combustible effective gas lost by pressure swing adsorption decarburization to generate heat, fundamentally avoids the emission of toxic and harmful substances, simultaneously recycles waste heat, saves energy, reduces consumption, greatly improves the scientificity and rationality of the production process, and achieves the purposes of energy conservation and environment protection.
In order to achieve the purpose, the invention provides the following technical scheme:
an energy-saving and environment-friendly novel synthetic ammonia desulfurization process comprises the following steps:
(1) firstly, introducing sulfur-containing semi-water gas into a sulfur-tolerant shift system, converting part of organic sulfur in the sulfur-containing semi-water gas by using a low-temperature sulfur-tolerant carbon monoxide shift catalyst, then introducing the converted organic sulfur into a PSA pressure swing adsorption desulfurization and decarbonization system, performing pressure alternation in a pressure swing adsorption tower in the PSA pressure swing adsorption desulfurization and decarbonization system to enable activated carbon pressure swing adsorption desulfurizer to play a role, and removing carbon dioxide and hydrogen sulfide together by using a vacuum pump;
(2) the combustible gas containing hydrogen sulfide, carbon dioxide, nitrogen and 3-5% of the loss of the PSA pressure swing adsorption desulfurization and decarburization system, which is extracted from the lower part of the pressure swing adsorption tower by a vacuum pump in the step (1), is sent into a gas making three-waste gas mixed combustion furnace, the hydrogen sulfide and oxygen react to generate sulfur dioxide and water at the high temperature of 900-;
(3) and (3) sending the sulfur dioxide generated by the reaction in the step (2) and other inert gases into a tail gas environment-friendly desulfurization system of a three-waste gas mixed combustion furnace for dedusting and desulfurization, washing the sulfur dioxide in a desulfurization tower by desulfurization liquid to generate calcium sulfite, further oxidizing the sulfur dioxide by an air blower to generate calcium sulfate products for sale to achieve the aim of desulfurization, and finally sending the generated tail gas to a 30-meter chimney to be subjected to online monitoring and then discharged up to the standard to achieve the aim of desulfurization.
Further, the catalyst in the step (1) consists of cobalt oxide with the mass fraction of 5 percent, molybdenum oxide with the mass fraction of 7 percent and the balance of carrier aluminum oxide; the conversion conditions are 200 ℃ and 350 ℃ and the humidity is 30 percent.
Further, the pressure alternation parameter in the step (1) is adsorption under the pressure of 0.8MPa and desorption under the vacuum pressure of-0.08 MPa.
Further, the combustible gas in the step (2) comprises 0.5-1% of hydrogen, 2-3% of carbon monoxide and 0.5-1% of methane by mass fraction.
Further, the environment-friendly tail gas treatment system of the three-waste gas mixed combustion furnace in the step (3) comprises an SNCR (selective non-catalytic reduction) denitration system, a pulse bag type dust removal system and a desulfurization system.
Further, the desulfurization solution in the step (3) is a mixed solution composed of 3-5% by mass of sodium hydroxide and 0.2-0.4% by mass of calcium hydroxide.
The invention has the beneficial effects that:
the invention optimizes the traditional desulfurization process, carries out secondary utilization, recycles combustible effective gas lost by pressure swing adsorption decarburization to generate heat, fundamentally stops the emission of toxic and harmful substances, simultaneously recycles waste heat, saves energy, reduces consumption, greatly improves the scientificity and rationality of the production process, and achieves the purposes of energy conservation and environmental protection.
Drawings
The above and other features, properties and advantages of the present invention will become more apparent from the following description of the embodiments with reference to the accompanying drawings in which like reference numerals denote like features throughout the several views, wherein:
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings:
embodiment 1 referring to fig. 1, a new energy-saving and environment-friendly synthetic ammonia desulfurization process comprises the following steps:
(1) firstly, introducing sulfur-containing semi-water gas into a sulfur-tolerant shift system, and introducing part of organic sulfur in the sulfur-containing semi-water gas into a PSA pressure swing adsorption desulfurization and decarbonization system after being converted by a low-temperature sulfur-tolerant carbon monoxide shift catalyst, wherein the catalyst consists of cobalt oxide with the mass fraction of 5%, molybdenum oxide with the mass fraction of 7% and the balance of aluminum oxide serving as a carrier; the conversion condition is that the temperature is 200 ℃ and 350 ℃ and the humidity is 30 percent; performing pressure alternation in a pressure swing adsorption tower in a PSA (pressure swing adsorption) desulfurization and decarbonization system to enable activated carbon pressure swing adsorption desulfurizer to play a role, and removing carbon dioxide and hydrogen sulfide together through a vacuum pump; wherein the pressure alternation parameter is adsorption under the pressure of 0.8MPa and desorption under the vacuum pressure of-0.08 MPa;
(2) the combustible gas containing hydrogen sulfide, carbon dioxide, nitrogen and 3-5% of the loss of the PSA pressure swing adsorption desulfurization and decarburization system, which is extracted from the lower part of the pressure swing adsorption tower by a vacuum pump in the step (1), is sent into a gas making three-waste gas mixed combustion furnace, the hydrogen sulfide and oxygen react to generate sulfur dioxide and water at the high temperature of 900-; wherein the combustible gas comprises 0.5-1% of hydrogen, 2-3% of carbon monoxide and 0.5-1% of methane by mass fraction;
(3) and (3) sending the sulfur dioxide generated by the reaction in the step (2) and other inert gases into a tail gas environment-friendly desulfurization system of a three-waste gas mixed combustion furnace for dedusting and desulfurization, washing the sulfur dioxide in a desulfurization tower by desulfurization liquid (the desulfurization liquid is a mixed solution consisting of 3-5% by mass of sodium hydroxide and 0.2-0.4% by mass of calcium hydroxide), so that the sulfur dioxide generates calcium sulfite, further oxidizing the calcium sulfite by a blower to generate a calcium sulfate product for sale, achieving the purpose of desulfurization, and finally sending the generated tail gas to a 30-meter chimney to be subjected to on-line monitoring and then discharged up to the standard, thereby achieving the purpose of desulfurization.
Wherein, three wastes gas co-combustion stove tail gas environmental protection processing system includes SNCR deNOx systems, pulse bag formula dust pelletizing system, desulfurization system, and specifically the working process is: quantitatively spraying ammonia water with certain concentration into the three-waste mixed combustion furnace to ensure that the ammonia reacts with the nitric oxide to generate nitrogen and water under certain conditions (850-; the dust is filtered in a bag type and left in a dust remover, and the dust is removed by timing pulse; the desulfurization process is that sulfur dioxide firstly reacts with sodium hydroxide to generate sodium sulfite, sodium sulfite solution is regenerated by calcium hydroxide to generate calcium sulfite precipitate, the sodium hydroxide is reduced to further purify the sulfur dioxide, and the generated calcium sulfite is oxidized by introducing air to generate calcium sulfate, namely a gypsum product.
The invention optimizes the traditional desulfurization process, carries out secondary utilization, recycles combustible effective gas lost by pressure swing adsorption decarburization to generate heat, fundamentally stops the emission of toxic and harmful substance hydrogen sulfide, simultaneously avoids secondary pollution of wet desulfurization byproduct sulfur paste to the environment, greatly improves the scientificity and rationality of the production process, and achieves the purposes of energy conservation and environmental protection.
It should be noted that the above-mentioned embodiments are only some of the preferred modes for implementing the invention, and not all of them. Obviously, all other embodiments obtained by persons of ordinary skill in the art based on the above-mentioned embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Claims (6)
1. The novel energy-saving and environment-friendly synthetic ammonia desulfurization process is characterized by comprising the following steps of:
(1) firstly, introducing sulfur-containing semi-water gas into a sulfur-tolerant shift system, converting part of organic sulfur in the sulfur-containing semi-water gas by using a low-temperature sulfur-tolerant carbon monoxide shift catalyst, then introducing the converted organic sulfur into a PSA pressure swing adsorption desulfurization and decarbonization system, performing pressure alternation in a pressure swing adsorption tower in the PSA pressure swing adsorption desulfurization and decarbonization system to enable activated carbon pressure swing adsorption desulfurizer to play a role, and removing carbon dioxide and hydrogen sulfide together by using a vacuum pump;
(2) the combustible gas containing hydrogen sulfide, carbon dioxide, nitrogen and 3-5% of the loss of the PSA pressure swing adsorption desulfurization and decarburization system, which is extracted from the lower part of the pressure swing adsorption tower by a vacuum pump in the step (1), is sent into a gas making three-waste gas mixed combustion furnace, the hydrogen sulfide and oxygen react to generate sulfur dioxide and water at the high temperature of 900-;
(3) and (3) sending the sulfur dioxide generated by the reaction in the step (2) and other inert gases into a tail gas environment-friendly desulfurization system for dedusting and desulfurization, washing the sulfur dioxide in a desulfurization tower by desulfurization liquid to generate calcium sulfite, further oxidizing the sulfur dioxide by an air blower to generate calcium sulfate products for sale, achieving the aim of desulfurization, and finally sending the generated tail gas to a 30-meter chimney to be subjected to on-line monitoring and then to be discharged after reaching the standard, so that the aim of desulfurization is achieved.
2. The new desulfurization process for synthetic ammonia according to claim 1, wherein the catalyst in step (1) comprises cobalt oxide 5% by mass, molybdenum oxide 7% by mass, and alumina as a carrier; the conversion conditions are 200 ℃ and 350 ℃ and the humidity is 30 percent.
3. The new process for desulfurizing synthetic ammonia according to claim 1, wherein the pressure alternation parameter in step (1) is adsorption at 0.8MPa and desorption at-0.08 MPa vacuum pressure.
4. The novel process for desulfurizing synthetic ammonia according to claim 1, wherein the composition of said combustible gas in step (2) is 0.5-1% by mass of hydrogen, 2-3% by mass of carbon monoxide and 0.5-1% by mass of methane.
5. The new desulfurization process for synthetic ammonia according to claim 1, wherein the environmental treatment system for tail gas of the three-waste gas mixed combustion furnace in step (3) comprises an SNCR (selective non-catalytic reduction) denitrification system, a pulse bag type dust removal system and a desulfurization system.
6. The novel process for desulfurizing synthetic ammonia according to claim 1, wherein the desulfurizing liquid in step (3) is a mixed solution of 3-5% by mass of sodium hydroxide and 0.2-0.4% by mass of calcium hydroxide.
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Citations (6)
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| CN104848208A (en) * | 2015-03-31 | 2015-08-19 | 浠水县福瑞德化工有限责任公司 | Three-waste mix combustion furnace production technology |
| CN107286012A (en) * | 2017-06-27 | 2017-10-24 | 金沂蒙集团有限公司 | A kind of energy-saving and purifying technique for synthesizing ammonia and anhydride cogeneration |
| CN109592639A (en) * | 2019-01-24 | 2019-04-09 | 华陆工程科技有限责任公司 | The technique of low hydrogen gas low-sulfur high carbon monoxide mine furnace exhaust gas separating-purifying carbon monoxide and hydrogen |
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2019
- 2019-11-14 CN CN201911112490.3A patent/CN110964575A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624540A (en) * | 2008-07-11 | 2010-01-13 | 李东田 | Process for separately desulfurizing and decarbonizing feed gases for coproduction of ammonia and alcohol |
| CN102134056A (en) * | 2010-01-22 | 2011-07-27 | 上海寰球石油化学工程有限公司 | Combined process for preparing power generation co-production synthesis ammonia feed gas by using crude gas containing CH4 |
| CN102320568A (en) * | 2011-08-25 | 2012-01-18 | 上海泽玛克敏达机械设备有限公司 | Method and device for preparing synthetic gas or hydrogen with BGL pressuring slag gasification and pure oxygen non-catalytic partial oxidation |
| CN104848208A (en) * | 2015-03-31 | 2015-08-19 | 浠水县福瑞德化工有限责任公司 | Three-waste mix combustion furnace production technology |
| CN107286012A (en) * | 2017-06-27 | 2017-10-24 | 金沂蒙集团有限公司 | A kind of energy-saving and purifying technique for synthesizing ammonia and anhydride cogeneration |
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Application publication date: 20200407 |