WO2025236231A1 - 一种硫酸生产中热能利用的工艺 - Google Patents

一种硫酸生产中热能利用的工艺

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Publication number
WO2025236231A1
WO2025236231A1 PCT/CN2024/093597 CN2024093597W WO2025236231A1 WO 2025236231 A1 WO2025236231 A1 WO 2025236231A1 CN 2024093597 W CN2024093597 W CN 2024093597W WO 2025236231 A1 WO2025236231 A1 WO 2025236231A1
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WO
WIPO (PCT)
Prior art keywords
heat exchanger
heat
sulfuric acid
flue gas
acid production
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/CN2024/093597
Other languages
English (en)
French (fr)
Inventor
赵志
刘纪状
韦光铭
唐海军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Sairui Technology Engineering Co Ltd
Original Assignee
Jiangsu Sairui Technology Engineering Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Sairui Technology Engineering Co Ltd filed Critical Jiangsu Sairui Technology Engineering Co Ltd
Publication of WO2025236231A1 publication Critical patent/WO2025236231A1/zh
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22—STEAM GENERATION
    • F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
    • F22B1/00—Methods of steam generation characterised by form of heating method
    • F22B1/02—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers
    • F22B1/18—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers the heat carrier being a hot gas, e.g. waste gas such as exhaust gas of internal-combustion engines
    • F22B1/1892—Systems therefor not provided for in F22B1/1807 - F22B1/1861
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22—STEAM GENERATION
    • F22D—PREHEATING, OR ACCUMULATING PREHEATED, FEED-WATER FOR STEAM GENERATION; FEED-WATER SUPPLY FOR STEAM GENERATION; CONTROLLING WATER LEVEL FOR STEAM GENERATION; AUXILIARY DEVICES FOR PROMOTING WATER CIRCULATION WITHIN STEAM BOILERS
    • F22D1/00—Feed-water heaters, i.e. economisers or like preheaters
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
    • F23G5/44—Details; Accessories
    • F23G5/46—Recuperation of heat
    • 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
    • F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2206/00—Waste heat recuperation
    • F23G2206/10—Waste heat recuperation reintroducing the heat in the same process, e.g. for predrying
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2206/00—Waste heat recuperation
    • F23G2206/20—Waste heat recuperation using the heat in association with another installation
    • F23G2206/203—Waste heat recuperation using the heat in association with another installation with a power/heat generating installation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2209/00—Specific waste
    • F23G2209/14—Gaseous waste or fumes
    • 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

Definitions

  • This invention relates to the field of thermal energy utilization technology, specifically a process for thermal energy utilization in sulfuric acid production.
  • this invention provides a process for further utilization of thermal energy in sulfuric acid production, which can transfer low-temperature thermal energy to high-temperature thermal energy, produce as much medium- and high-pressure steam as possible, and generate more economic benefits.
  • a process for utilizing heat energy in sulfuric acid production is designed, in which a first heat exchanger and/or a second heat exchanger and/or a third heat exchanger are added to the sulfuric acid production process.
  • the first heat exchanger 1-1 heats the air entering the sulfur incinerator.
  • the heated air then enters the sulfur incinerator, and the flue gas after combustion enters the waste heat boiler.
  • the high-temperature heat in the flue gas is transferred to the steam system in the waste heat boiler to generate medium and high-pressure steam.
  • the second heat exchanger 2-1 heats the flue gas coming out of the HRS tower.
  • the heated flue gas enters the hot and cold heat exchanger to exchange heat with the flue gas coming out of the third stage of the converter, and is further heated to meet the process requirements. This reduces the heat consumed by the other flue gas coming out of the hot and cold heat exchanger.
  • the heat energy is then transferred to the steam system for utilization by heating high-pressure hot water through the economizer 3A.
  • the third heat exchanger 3-1 heats the boiler feedwater from the boiler feedwater pump before it enters the economizer 3A and/or economizer 4B, or it serves as a heat source for the first heat exchanger 1-1 and the second heat exchanger 2-1 before entering the economizer 3A and/or economizer 4B.
  • the increased heat from this portion of the boiler feedwater is used to generate medium and high pressure steam.
  • the first heat exchanger is installed before the inlet of the sulfur incinerator, the second heat exchanger is installed between the HRS tower and the hot and cold heat exchanger, and the third heat exchanger is installed between the boiler feedwater pump and the economizer.
  • Temperature detection points and control valves are provided after the first, second, and third heat exchangers. The temperature is controlled by adjusting the amount of material entering the heat exchanger according to the set temperature parameters.
  • the heating medium in the first and second heat exchangers is one or more of the following: high-temperature sulfuric acid, high-pressure hot water, high-pressure steam, low-pressure steam, and external heat sources generated during the sulfuric acid production process.
  • the heat source of the third heat exchanger comes from the high-temperature sulfuric acid produced by the HRS tower.
  • the high-temperature sulfuric acid enters the heat source medium inlet of the third heat exchanger to exchange heat with the boiler feedwater, and then flows out from the heat source medium outlet of the third heat exchanger.
  • the materials in the first, second, and third heat exchangers that come into contact with high-temperature acid are made of acid-resistant stainless steel, while the materials that come into contact with hot water and steam are made of carbon steel.
  • the sulfuric acid production processes mentioned above include, but are not limited to, sulfuric acid production from sulfur, sulfuric acid production from pyrite, and sulfuric acid production from smelting flue gas.
  • this invention adds three sets of heat exchangers. Each set can be used individually or in combination, allowing for flexible configuration based on different application scenarios and objects, significantly increasing the output of medium and high-pressure steam. It also maximizes the use of high-temperature sulfuric acid, hot water, steam, flue gas from the sulfuric acid production process, or energy sources outside the process, as heat sources, thereby improving heat energy recovery and utilization rates.
  • Figure 1 is a process flow diagram of flue gas and acid system in the sulfuric acid production process of the present invention.
  • Figure 2 is a process flow diagram of water and steam in the sulfuric acid production process of the present invention.
  • 1-1 is the first heat exchanger
  • 2-1 is the second heat exchanger
  • 3-1 is the third heat exchanger
  • 4-1 is liquid sulfur
  • 4-2 is air
  • 4-3 is an air filter
  • 4-4 is a drying tower
  • 4-5 is the main fan
  • 4-6 is the sulfur incinerator
  • 4-7 is the waste heat boiler
  • 4-8 is the converter
  • 4-9 is the high-temperature superheater 1B
  • 4-10 is a hot-to-hot heat exchanger
  • 4-11 is a cold-to-hot heat exchanger.
  • the components are as follows: 4-12 is economizer 3A, 4-13 is ejector, 4-14 is low-pressure steam, 4-15 is HRS tower, 4-16 is HRS acid circulation pump, 4-17 is superheater 4A, 4-18 is economizer 4B, 4-19 is economizer 4A, 4-20 is secondary suction tower, 4-21 is tail suction device, 4-22 is secondary suction acid pump tank, 4-23 is secondary suction acid cooler, and 4-24 is finished acid cooler.
  • the equipment is as follows: 4-25 is finished acid, 4-26 is HRS boiler, 4-27 is HRS heater, 4-28 is HRS diluter, 4-29 is another HRS heater, 4-30 is dried acid pump tank, 4-31 is dried acid cooler, 4-32 is pump tank dilution water, 4-33 is HRS dilution water, 4-34 is demineralized water (0.4 MPa), 4-35 is deaerator, 4-36 is boiler feed water pump, 4-37 is boiler chemical dosing device, 4-38 is medium and high pressure superheated steam, 4-39 is continuous blowdown expander, 4-40 is periodic blowdown expander, 4-41 is vent, 4-42 is blowdown outlet, 4-43 is low pressure saturated steam, 4-44 is low pressure jet steam, 4-45 is HRS blowdown tank, 4-46 is another vent, 4-47 is another blowdown outlet, and 4-48 is low pressure steam.
  • this invention relates to a process for utilizing heat energy in sulfuric acid production. Specifically, it involves adding a first heat exchanger 1-1 and/or a second heat exchanger 2-1 and/or a third heat exchanger 3-1 to the existing sulfuric acid production process.
  • the first heat exchanger 1-1 heats the air entering the sulfur incinerator from 60 ⁇ 130°C to 180 ⁇ 280°C.
  • the heated air enters the sulfur incinerator, and the flue gas after combustion enters the waste heat boiler, transferring the high-temperature heat in the flue gas to the steam system in the waste heat boiler (i.e., the water vapor in serial number 118 in Figure 2), generating more medium and high-pressure steam.
  • the second heat exchanger 2-1 heats the flue gas (18) from the HRS tower from 70-90°C to 100-190°C.
  • the heated flue gas (19) then enters the hot and cold heat exchanger to exchange heat with the flue gas (14) from the outlet of the third stage of the converter, further raising its temperature to about 330°C (20), meeting the process requirements.
  • the flue gas (14) from the outlet of the third stage of the converter has a temperature of 450-470°C.
  • the flue gas (15) has a temperature of about 310-350°C. In the traditional process, the temperature here is usually about 250-280°C, which is 60-100°C higher.
  • the heat that is higher than the temperature in the improved process of this invention is the heat transferred and utilized from the low-temperature heat source. This part of the heat is absorbed and utilized by the economizer 3A to generate more medium and high-pressure steam.
  • the third heat exchanger 3-1 heats the boiler feedwater (serial number 110) from the boiler feedwater pump from 104°C ⁇ 135°C to 145 ⁇ 150°C before it enters economizer 3A and/or economizer 4B, or it serves as a heat source for the first heat exchanger 1-1 and the second heat exchanger 2-1 before entering economizer 3A and/or economizer 4B. This increases the temperature and heat of the boiler feedwater reaching the economizers, ultimately increasing the production of medium and high-pressure steam.
  • the equipment for sulfuric acid production includes a drying tower, a blower, a sulfur incinerator, a converter, and an HRS (High-Speed Reduction) tower.
  • the drying tower inlet is connected to an air filter, and the drying tower outlet is connected to one end of the main blower.
  • the other end of the main blower is connected to the inlet of the sulfur incinerator.
  • the sulfur incinerator outlet is connected to the inlet of the waste heat boiler.
  • the waste heat boiler outlet is connected to the inlet of the first stage of the converter.
  • the outlet of the first stage of the converter is connected to the inlet of the high-temperature superheater 1B.
  • the outlet of the high-temperature superheater 1B is connected to the inlet of the second stage of the converter.
  • the outlet of the second stage of the converter is connected to the first inlet of the hot-to-hot heat exchanger.
  • the first outlet of the hot-to-hot heat exchanger is connected to the inlet of the third stage of the converter.
  • the outlet of the third stage of the converter is connected to the first inlet of the cold-to-hot heat exchanger.
  • the first outlet of the cold-to-hot heat exchanger is connected to the inlet of the economizer 3A.
  • the outlet of the economizer 3A is connected to the flue gas inlet of the HRS absorption tower.
  • the flue gas outlet of the HRS absorption tower is connected to the cold-to-hot heat exchanger.
  • the second inlet of the heat exchanger is connected to the second outlet of the cold heat exchanger, which is connected to the second inlet of the hot heat exchanger.
  • the second outlet of the hot heat exchanger is connected to the four inlets of the converter.
  • the four outlets of the converter are connected to the inlet of the second absorption tower via superheater 4A, economizer 4B, and economizer 4A, respectively.
  • the flue gas outlet of the second absorption tower is connected to the tail suction device.
  • the acid outlet of the second absorption tower is connected to the second absorption acid pump tank.
  • the acid side outlet of the HRS absorption tower pump tank is connected to the inlet of the HRS boiler via the HRS acid circulation pump.
  • the outlet of the HRS boiler is connected to the inlet of the HRS heater and the inlet of the HRS diluter, respectively.
  • the outlet of the HRS heater is connected to the acid side inlet of the HRS preheater.
  • the acid outlet of the HRS preheater is connected to the second absorption acid pump tank.
  • the acid outlet of the second absorption acid pump tank enters the inlet of the finished acid cooler.
  • the finished acid is obtained from the outlet of the finished acid cooler.
  • air is filtered through an air filter, and the filtered air enters a drying tower for drying.
  • the dried air is then pressurized by a fan and enters a sulfur incinerator, where it burns and reacts with liquid sulfur to produce high-temperature SO2 flue gas.
  • This flue gas then enters a waste heat boiler, where the high-temperature heat is transferred to the steam system, generating medium- and high-pressure steam.
  • the flue gas After exiting the waste heat boiler, the flue gas enters a converter for catalytic oxidation. After exiting the converter's third-stage outlet, the flue gas is cooled by a heat exchanger and economizer 3A before entering the HRS tower for SO3 absorption. The flue gas exits the HRS tower. The flue gas passes through a cold heat exchanger and a hot heat exchanger before entering the fourth stage of the converter for further catalytic oxidation.
  • the flue gas exiting the fourth stage of the converter is cooled by superheater 4A, economizer 4B, and economizer 4A before entering the second absorption tower for secondary SO3 absorption.
  • the high-temperature sulfuric acid produced by the HRS tower passes through the HRS boiler and the third heat exchanger, then merges and splits into two paths. One part enters the HRS heater and then enters the second absorption acid pump tank to react and generate sulfuric acid, which then passes through the finished acid cooler to obtain the finished acid.
  • the other part of the high-temperature sulfuric acid passes through the HRS diluter, is diluted with water and acid, and then returns to the HRS tower to repeat the absorption process.
  • the first heat exchanger 1-1 is installed before the inlet of the sulfur incinerator, the second heat exchanger 2-1 is installed between the HRS tower and the hot and cold heat exchanger, and the third heat exchanger 3-1 is installed between the boiler feed pump and the economizer.
  • Temperature detection points and control valves are installed after the first heat exchanger 1-1, the second heat exchanger 2-1, and the third heat exchanger 3-1. The temperature is controlled by adjusting the amount of material entering the heat exchanger according to the set temperature parameters.
  • the heating medium in the first heat exchanger 1-1 and the second heat exchanger 2-1 is one or more of the following: high-temperature sulfuric acid, high-pressure hot water, high-pressure steam, and low-pressure steam generated in the sulfuric acid production process.
  • heat sources outside the sulfuric acid production process can also be utilized.
  • the sources of high-temperature sulfuric acid include one or more of the flue gas (numbered 64, 66, 68, 72, and 73 in Figure 1).
  • the sources of high-pressure hot water include one or more of the following (numbered 111 and 113 in Figure 2).
  • the sources of high-pressure steam include one or more of the following (numbered 119 and 120 in Figure 2).
  • the source of high-pressure steam is also shown in Figure 2 (numbered 125).
  • the heat source for the third heat exchanger 3-1 comes from high-temperature sulfuric acid (serial number 67) produced by the HRS tower, with a temperature of 200 ⁇ 230°C.
  • the high-temperature sulfuric acid serves as the heat source medium for the third heat exchanger, transferring heat to the high-pressure boiler feedwater (serial number 110), and then flowing out from the heat source medium outlet of the third heat exchanger.
  • the first heat exchanger 1-1 is an air heater
  • the second heat exchanger 2-1 is a flue gas heater
  • the third heat exchanger 3-1 is an HRS high-pressure heater.
  • the materials that come into contact with high-temperature acid are made of acid-resistant stainless steel, while the materials that come into contact with hot water and steam are made of carbon steel.
  • the flue gas (15) heated by the second heat exchanger 2-1 exits from the hot and cold heat exchanger, reducing the heat consumed by the other flue gas exiting from the hot and cold heat exchanger, and heats the high-pressure hot water (112) through the economizer 3A, transferring the heat energy to the steam system for utilization.
  • Sulfuric acid production processes include, but are not limited to, sulfuric acid production from sulfur, sulfuric acid production from pyrite, and sulfuric acid production from smelting flue gas.
  • a first heat exchanger 1-1 is added to the existing sulfuric acid production process.
  • the high-temperature sulfuric acid obtained from the HRS tower is used to heat the air entering the sulfur incinerator, transferring the low-temperature heat energy to the medium and high-pressure steam system.
  • the heat from the third heat exchanger 3-1 (serial number 111) in the system is used to heat the air in the sulfur combustion furnace, transferring the low-temperature heat energy to the subsequent medium and high-pressure steam system.
  • the air entering the sulfur incinerator is heated by a heat source generated by an external device, and the low-temperature heat energy is transferred to the subsequent medium and high-pressure steam system.
  • a second heat exchanger 2-1 is added to the existing sulfuric acid production process.
  • the high-temperature sulfuric acid obtained from the HRS tower is used to heat the flue gas at the outlet of the HRS tower, transferring the low-temperature heat energy to the medium and high-pressure steam system.
  • the waste heat of the flue gas in the system is used to heat the flue gas at the outlet of the HRS tower, transferring the low-temperature heat energy to the medium and high-pressure steam system.
  • the flue gas at the outlet of the HRS tower is heated by a heat source generated by an external device, and the low-temperature heat energy is transferred to the medium and high-pressure steam system.
  • a third heat exchanger 3-1 is added to the existing sulfuric acid production process.
  • the high-temperature sulfuric acid obtained through the HRS tower heats the feedwater of the medium and high-pressure boilers, transferring the low-temperature heat energy to the subsequent medium and high-pressure steam system.
  • a first heat exchanger 1-1 and a second heat exchanger 2-1 are added to the existing sulfuric acid production process.
  • the high-temperature sulfuric acid obtained through the HRS tower is used to heat the air entering the sulfur incinerator and/or the flue gas exiting the HRS tower, transferring low-temperature heat energy to the medium- and high-pressure steam system.
  • high-temperature sulfuric acid obtained from the HRS tower is used to generate low-pressure steam, which is then used to heat the air entering the sulfur incinerator and/or the flue gas at the outlet of the HRS tower, transferring low-temperature heat energy to the medium- and high-pressure steam system.
  • Embodiment 1 [Corrected according to Rule 91, 07.08.2024]
  • a third heat exchanger is added to the sulfuric acid production process.
  • the high-temperature sulfuric acid obtained through the HRS tower heats the feedwater of the medium and high-pressure boilers, transferring the low-temperature heat energy to the subsequent medium and high-pressure steam system.
  • Embodiment 2 [Corrected according to Rule 91, 07.08.2024]
  • a third heat exchanger is added to the sulfuric acid production process.
  • the high-temperature sulfuric acid obtained through the HRS tower heats the feedwater of the medium and high-pressure boilers, transferring the low-temperature heat energy to the subsequent medium and high-pressure steam system.
  • Embodiment 4 The difference between this embodiment and Embodiment 4 is that a third heat exchanger is added to the sulfuric acid production process.
  • the high-temperature sulfuric acid obtained through the HRS tower heats the feedwater of the medium and high-pressure boilers, transferring the low-temperature heat energy to the subsequent medium and high-pressure steam system.
  • This invention adds three sets of heat exchangers, each of which can be used individually or in combination, allowing for flexible configuration based on different application scenarios and targets, significantly increasing the output of medium and high-pressure steam. It maximizes the use of high-temperature sulfuric acid, hot water, steam, and flue gas from the sulfuric acid production process as heat sources, improving heat energy recovery and utilization rates. By setting up a heat exchange system to transfer low-temperature heat energy to the high-temperature heat energy system, it can achieve 1.41 ⁇ 1.55 t/t of medium and high-pressure steam and 0.31 ⁇ 0.26 t/t of low-pressure steam for acid, maximizing economic benefits.

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Abstract

一种硫酸生产中热能利用的工艺，硫酸生产工艺中增设第一换热器（1-1）和/或第二换热器（2-1）和/或第三换热器（3-1），第一换热器（1-1）将进入焚硫炉的空气加热，将烟气中的高温热量转移至废热锅炉中的蒸汽系统内，产生中、高压蒸汽；第二换热器（2-1）将从HRS塔出来的烟气加热，加热后的烟气进入冷热换热器与从转化器三段出口来的烟气进行换热进一步升温达到工艺要求；第三换热器（3-1）将从锅炉给水泵来的锅炉给水加热后进入省煤器3A和/或省煤器4B，这部分锅炉给水增加的热量用于产生中、高压蒸汽。同现有技术相比，增加三套换热器，根据使用场景、对象不同做灵活配置，显著提高中、高压蒸汽的产量。

Description

一种硫酸生产中热能利用的工艺 技术领域
[根据细则91更正 07.08.2024]
   本发明涉及热能利用技术领域，具体地说是一种硫酸生产中热能利用的工艺。
 背景技术
[根据细则91更正 07.08.2024]
目前，硫酸工业的热能回收系统是否高效是整个装置的重中之重，目前硫磺制酸装置的吨酸产汽量在：3.0~9.8MPa，400~540℃的中、高压蒸汽中为1.25~1.32t/t，0.6~1.0MPa，饱和蒸汽的低温热回收系统，简称HRS（Heat Recovery Systems），产低压蒸汽~0.45t/t；在市场上这两种蒸汽的价格差距较大；因此，尽量提高中、高压蒸汽产量，产生更多的经济效益是硫酸工业的迫切追求。
 发明内容
[根据细则91更正 07.08.2024]
本发明为克服现有技术的不足，提供一种硫酸生产中热能进一步利用的工艺，能够将低温位热能向高温位热能转移，尽可能的多产中、高压蒸汽，产生更多的经济效益。
[根据细则91更正 07.08.2024]
为实现上述目的，设计一种硫酸生产中热能利用的工艺，硫酸生产工艺中增设第一换热器和/或第二换热器和/或第三换热器，
[根据细则91更正 07.08.2024]
第一换热器1-1将进入焚硫炉的空气加热，加热后的空气进入焚硫炉，经过燃烧反应后的烟气进入废热锅炉，将烟气中的高温热量转移至废热锅炉中的蒸汽系统内，产生中、高压蒸汽；
[根据细则91更正 07.08.2024]
第二换热器2-1将从HRS塔出来的烟气加热，加热后的烟气进入冷热换热器与从转化器三段出口来的烟气进行换热进一步升温达到工艺要求，减少另一股从冷热换热器出来的烟气消耗的热量，并通过省煤器3A加热高压热水，将热能转移至蒸汽系统中加以利用； 
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第三换热器3-1将从锅炉给水泵来的锅炉给水加热后进入省煤器3A和/或省煤器4B，或作为第一换热器1-1、第二换热器2-1的热源后再进入省煤器3A和/或省煤器4B，这部分锅炉给水增加的热量用于产生中、高压蒸汽。
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所述的第一换热器安装在焚硫炉入口前，第二换热器安装在HRS塔与冷热换热器之间，第三换热器的安装在锅炉给水泵和省煤器之间。
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所述的第一换热器、第二换热器、第三换热器后都设有温度检测点和控制阀门，根据设定温度参数调节进入换热器的物料量来控制温度。
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所述的第一换热器、第二换热器内加热介质的来源为硫酸生产工艺中产生的高温硫酸、高压热水、高压蒸汽、低压蒸汽、外界热源中的一种或多种。
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所述的第三换热器的热源来自HRS塔产生的高温硫酸，高温硫酸进入第三换热器的热源介质入口将热量换热给锅炉给水，再从第三换热器的热源介质出口流出。
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所述的第一换热器、第二换热器、第三换热器中与高温酸接触的材料选用耐酸不锈钢，与热水、蒸汽接触的材料选用碳钢。
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所述的第二换热器升温后的烟气从冷热换热器出来，减少了另一股从冷热换热器出来的烟气消耗的热量，并通过省煤器3A加热高压热水，将热能转移至蒸汽系统中加以利用。
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所述的硫酸生产工艺包括但不限于硫磺制酸，硫铁矿制酸，冶炼烟气制酸。
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本发明同现有技术相比，增加三套换热器，每套换热器可以单独使用，也可以任意组合、联合使用，根据使用场景、对象不同做灵活配置，显著提高中、高压蒸汽的产量。尽可能利用硫酸生产工艺中的高温硫酸、热水、蒸汽、烟气或硫酸生产工艺外的能源作为热源，提高热能回收利用率。
 附图说明
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图1为本发明硫酸生产工艺中烟气和酸系统工艺流程图。
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图2为本发明硫酸生产工艺中水、汽工艺流程图。
 具体实施方式
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参见图1至图2中，其中1-1是第一换热器，2-1是第二换热器，3-1是第三换热器，4-1是液态硫磺，4-2是空气，4-3是空气过滤器，4-4是干燥塔，4-5是主风机，4-6是焚硫炉，4-7是废热锅炉，4-8是转化器，4-9是高温过热器1B，4-10是热热换热器，4-11是冷热换热器，4-12是省煤器3A，4-13是喷射器，4-14是低压蒸汽，4-15是HRS塔，4-16是HRS酸循环泵，4-17是过热器4A，4-18是省煤器4B，4-19是省煤器4A，4-20是二吸塔，4-21是尾吸装置，4-22是二吸酸泵槽，4-23是二吸酸冷却器，4-24是成品酸冷却器，4-25是成品酸，4-26是HRS锅炉，4-27是HRS加热器，4-28是HRS稀释器，4-29是另一HRS加热器，4-30是干燥酸泵槽，4-31是干燥酸冷却器，4-32是泵槽稀释水，4-33是HRS稀释水，4-34是脱盐水（0.4Mpa），4-35是除氧器，4-36是锅炉给水泵，4-37是锅炉加药装置，4-38是中、高压过热蒸汽，4-39是连续排污膨胀器，4-40是定期排污膨胀器，4-41是放空口，4-42是排污口，4-43是低压饱和蒸汽，4-44是低压喷射蒸汽，4-45是HRS排污罐，4-46是另一放空口，4-47是另一排污口，4-48是低压蒸汽。
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下面根据附图对本发明做进一步的说明。
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如图1至图2所示，本发明是一种硫酸生产中热能利用的工艺，具体的说是在现有的硫酸生产工艺中增设第一换热器1-1和/或第二换热器2-1和/或第三换热器3-1，
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第一换热器1-1将进入焚硫炉的空气从60~130℃加热到180~280℃，加热后的空气进入焚硫炉，经过燃烧反应后的烟气进入废热锅炉，将烟气中的高温热量转移至废热锅炉（即图2中序号118的水汽）中的蒸汽系统内，产生更多的中、高压蒸汽。
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第二换热器2-1将从HRS塔出来的烟气（序号18）从70~90℃加热到100~190℃，加热后的烟气（序号19）进入冷热换热器与从转化器三段出口来的烟气（序号14）进行换热进一步升温到330℃左右（序号20），达到工艺要求；转化器三段出口来的烟气（序号14）温度为450~470℃，经过冷热换热器换热后的烟气（序号15）的温度约310~350℃，传统工艺中此处的温度通常约250~280℃左右，高出60~100℃，本发明改进后的工艺比传统工艺温度高出来的部分的热量就是从低温位热源中被转移利用的热量，这部分热量通过省煤器3A吸收利用，产生更多的中、高压蒸汽。
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第三换热器3-1将从锅炉给水泵来的锅炉给水（序号110）从104℃~135℃加热到145~150℃后进入省煤器3A和/或省煤器4B，或作为第一换热器1-1、第二换热器2-1的热源后再进入省煤器3A和/或省煤器4B。提高了到省煤器的锅炉给水温度和热量，最终提高了中、高压蒸汽产量。
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硫酸生产工艺的设备包括干燥塔、风机、焚硫炉、转化器、HRS塔，干燥塔入口连接空气过滤器，干燥塔出口连接主风机的一端，主风机的另一端与焚硫炉的入口连接，焚硫炉的出口连接废热锅炉的入口，废热锅炉的出口连接转化器的一段入口，转化器一段出口连接高温过热器1B的入口，高温过热器1B的出口连接转化器二段入口，转化器二段出口连接热热换热器的第一入口，热热换热器的第一出口连接转化器三段入口，转化器三段出口连接冷热换热器的第一入口，冷热换热器的第一出口连接省煤器3A的入口，省煤器3A的出口连接HRS吸收塔的烟气入口，HRS吸收塔的烟气出口与冷热换热器的第二入口相连，冷热换热器的第二出口连接热热换热器的第二入口，热热换热器的第二出口连接转化器的四段入口，转化器的四段出口连接分别通过过热器4A、省煤器4B、省煤器4A连接二吸塔的入口，二吸塔的烟气出口连接尾吸装置，二吸塔的酸出口连接二吸酸泵槽，HRS吸收塔泵槽的酸侧出口通过HRS酸循环泵连接HRS锅炉的入口，HRS锅炉的出口分别连接HRS加热器的入口、HRS稀释器的入口，HRS加热器的出口连接HRS预热器酸侧进口，HRS预热器酸出口连接到二吸酸泵槽，二吸酸泵槽的出酸部分进入成品酸冷却器的入口，成品酸冷却器的出口得到成品酸。硫酸生产工艺中，空气通过空气过滤器过滤，过滤后的空气进入干燥塔内干燥，接着干燥空气通过风机加压进入焚硫炉，与液态硫磺在焚硫炉内燃烧、反应产生高温的SO2烟气，烟气进入废热锅炉，将烟气中的高温热量转移至废热锅炉中的蒸汽系统内，产生中、高压蒸汽，烟气从废热锅炉出来后进入转化器催化氧化，烟气从转化器三段出口出来后通过冷热换热器、省煤器3A的降温后进入HRS塔进行SO3吸收，HRS塔烟气出口的烟气经过冷热换热器、热热换热器后进入转化器四段再次催化氧化，转化器四段出口烟气经过过热器4A、省煤器4B、省煤器4A降温后，进入二吸塔进行SO3的二次吸收，HRS塔产生的高温硫酸分别通过HRS锅炉和第三换热器后汇合再分两路，一部分进入HRS加热器后进入二吸酸泵槽中反应生成硫酸，再通过成品酸冷却器，得到成品酸，另一部分高温硫酸经过HRS稀释器，加水和串酸稀释再回到HRS塔重复吸收流程。
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第一换热器1-1安装在焚硫炉入口前，第二换热器2-1安装在HRS塔与冷热换热器之间，第三换热器3-1的安装在锅炉给水泵和省煤器之间。
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第一换热器1-1、第二换热器2-1、第三换热器3-1后道设有温度检测点和控制阀门，根据设定温度参数调节进入换热器的物料量来控制温度。
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第一换热器1-1、第二换热器2-1内加热介质的来源为硫酸生产工艺中产生的高温硫酸、高压热水、高压蒸汽、低压蒸汽中的一种或多种。具体使用时，还可以或利用硫酸生产工艺外的热源。其中高温硫酸来源包括图1中序号64、序号66、序号68、序号72、序号73烟气的一种或多种。高压热水来源包括图2中序号111、序号113的一种或多种。高压蒸汽来源包括图2中序号119、序号120的一种或多种。高压蒸汽来源包括图2中序号125。
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第三换热器3-1的热源来自HRS塔产生的高温硫酸（序号67），温度为200~230℃，高温硫酸作为第三换热器的热源介质，将热量换热给高压锅炉给水（序号110），再从第三换热器的热源介质出口流出。
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第一换热器1-1为空气加热器，第二换热器2-1为烟气加热器，第三换热器3-1为HRS高压加热器。
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第一换热器1-1、第二换热器2-1、第三换热器3-1中与高温酸接触的材料选用耐酸不锈钢，与热水、蒸汽接触的材料选用碳钢。
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本实施例中，第二换热器2-1升温后的烟气（序号15）从冷热换热器出来，减少了另一股从冷热换热器出来的烟气消耗的热量，并通过省煤器3A加热高压热水（序号112），将热能转移至蒸汽系统中加以利用。
实施例一
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硫酸生产工艺包括但不限于硫磺制酸，硫铁矿制酸，冶炼烟气制酸。
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本实施例中，在现有的硫酸生产工艺中增设第一换热器1-1，通过HRS塔得到的高温硫酸去加热进焚硫炉的空气，将低温位热能转移至中、高压蒸汽系统中。
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在本实施例的另一实施例中，通过系统中的第三换热器3-1部分的热量（序号111）去加热焚硫炉空气，将低温位热能转移至后续的中、高压蒸汽系统中。
实施例二
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在本实施例的另一实施例中，利用外部设备产生的热源加热进焚硫炉空气，将低温位热能转移至后续的中、高压蒸汽系统中。
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本实施例中，在现有的硫酸生产工艺中增设第二换热器2-1。通过HRS塔得到的高温硫酸去加热HRS塔出口的烟气，将低温位热能转移至中、高压蒸汽系统中。
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在本实施例的另一实施例中，通过系统中的烟气余热去加热HRS塔出口的烟气，将低温位热能转移至中、高压蒸汽系统中。
实施例三
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在本实施例的另一实施例中，利用外部设备产生的热源加热HRS塔出口的烟气，将低温位热能转移至中、高压蒸汽系统中。
实施例四
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本实施例中，在现有的硫酸生产工艺中增设第三换热器3-1。通过HRS塔得到的高温硫酸加热中、高压锅炉给水，将低温位热能转移至后续的中、高压蒸汽系统中。
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本实施例中，在现有的硫酸生产工艺中增设第一换热器1-1和第二换热器2-1。 通过HRS塔得到的高温硫酸去加热进焚硫炉空气和/或HRS塔出口的烟气，将低温位热能转移至中、高压蒸汽系统中。
实施例五
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在本实施例的另一实施例中，通过HRS塔得到的高温硫酸去产生低压蒸汽，再通过低压蒸汽加热进焚硫炉空气和/或HRS塔出口的烟气，将低温位热能转移至中、高压蒸汽系统中。
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本实施例仅说明于实施例一的不同之处，相同之处不再重复说明。
实施例六
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本实施例与实施例一的不同之处在于，本实施例在硫酸生产工艺中增设第三换热器。通过HRS塔得到的高温硫酸加热中、高压锅炉给水，将低温位热能转移至后续的中、高压蒸汽系统中。
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本实施例仅说明于实施例二的不同之处，相同之处不再重复说明。
实施例七
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本实施例与实施例二的不同之处在于，本实施例在硫酸生产工艺中增设第三换热器。通过HRS塔得到的高温硫酸加热中、高压锅炉给水，将低温位热能转移至后续的中、高压蒸汽系统中。
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本实施例仅说明于实施例四的不同之处，相同之处不再重复说明。
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本实施例与实施例四的不同之处在于，本实施例在硫酸生产工艺中增设第三换热器。通过HRS塔得到的高温硫酸加热中、高压锅炉给水，将低温位热能转移至后续的中、高压蒸汽系统中。
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本发明增加三套换热器，每个换热器可以单独使用，也可以任意组合、联合使用，根据使用场景、对象不同做灵活配置，显著提高中、高压蒸汽的产量。尽可能利用硫酸生产工艺中的高温硫酸、热水、蒸汽、烟气作为热源，提高热能回收利用率。通过设置换热系统，将低温位热能转移至高温位热能系统中，可实现中、高压蒸汽1.41~1.55t/t酸，同时低压蒸汽0.31~0.26t/t酸，最大化的提高经济效益。

Claims (8)

  1. 一种硫酸生产中热能利用的工艺，其特征在于：硫酸生产工艺中增设第一换热器（1-1）和/或第二换热器（2-1）和/或第三换热器（3-1），
    第一换热器（1-1）将进入焚硫炉的空气加热，加热后的空气进入焚硫炉，经过燃烧反应后的烟气进入废热锅炉，将烟气中的高温热量转移至废热锅炉中的蒸汽系统内，产生中、高压蒸汽；
    第二换热器（2-1）将从HRS塔出来的烟气加热，加热后的烟气进入冷热换热器与从转化器三段出口来的烟气进行换热进一步升温达到工艺要求，减少另一股从冷热换热器出来的烟气消耗的热量，并通过省煤器3A加热高压热水，将热能转移至蒸汽系统中加以利用；
    第三换热器（3-1）将从锅炉给水泵来的锅炉给水加热后进入省煤器3A和/或省煤器4B，或作为第一换热器1-1、第二换热器2-1的热源后再进入省煤器3A和/或省煤器4B，这部分锅炉给水增加的热量用于产生中、高压蒸汽。
  2. 根据权利要求1所述的一种硫酸生产中热能利用的工艺，其特征在于：所述的第一换热器（1-1）安装在焚硫炉入口前，第二换热器（2-1）安装在HRS塔与冷热换热器之间，第三换热器（3-1）安装在锅炉给水泵和省煤器之间。
  3. 根据权利要求1所述的一种硫酸生产中热能利用的工艺，其特征在于：所述的第一换热器（1-1）、第二换热器（2-1）、第三换热器（3-1）后都设有温度检测点和控制阀门，根据设定温度参数调节进入换热器的物料量来控制温度。
  4. 根据权利要求1所述的一种硫酸生产中热能利用的工艺，其特征在于：所述的第一换热器（1-1）、第二换热器（2-1）内加热介质的来源为硫酸生产工艺中产生的高温硫酸、高压热水、高压蒸汽、低压蒸汽、外界热源中的一种或多种。
  5. 根据权利要求1所述的一种硫酸生产中热能利用的工艺，其特征在于：所述的第三换热器（13-1）的热源来自HRS塔产生的高温硫酸，高温硫酸进入第三换热器（3-1）的热源介质入口将热量换热给锅炉给水，再从第三换热器的热源介质出口流出。
  6. 根据权利要求1所述的一种硫酸生产中热能利用的工艺，其特征在于：所述的第一换热器（1-1）、第二换热器（2-1）、第三换热器（3-1）中与高温酸接触的材料选用耐酸不锈钢，与热水、蒸汽接触的材料选用碳钢。
  7. 根据权利要求1所述的一种硫酸生产中热能利用的工艺，其特征在于：所述的第二换热器（2-1）升温后的烟气从冷热换热器出来，减少了另一股从冷热换热器出来的烟气消耗的热量，并通过省煤器3A加热高压热水，将热能转移至蒸汽系统中加以利用。
  8. 根据权利要求1所述的一种硫酸生产中热能利用的工艺，其特征在于：所述的硫酸生产工艺包括但不限于硫磺制酸，硫铁矿制酸，冶炼烟气制酸。
PCT/CN2024/093597 2024-05-14 2024-05-16 一种硫酸生产中热能利用的工艺 Pending WO2025236231A1 (zh)

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