阅读说明：本技术 一种兰炭炉生产氢气、氮气、一氧化碳的方法 (Method for producing hydrogen, nitrogen and carbon monoxide by semi-coke furnace ) 是由 田森林 杨芬 赵群 张秋林 杨皓 杨鹏 宁平 于 2021-07-11 设计创作，主要内容包括：本发明公开了一种兰炭炉生产氢气、一氧化碳、氮气的方法,所述方法为将兰炭尾气分离液体物质后得到原料气,采用工作压力-0.05～0.1MPa变压吸附分离原料气,吸附塔低压解吸端获得水、二氧化碳、不饱和烃类、酚类气体、C-2～(+)、甲烷为循环气,吸附塔高压端获得氢气、氩气、氧气、氮气、一氧化碳为产品气,将循环气送入兰炭燃烧室作为燃料,同时送入富氧空气作为助燃剂,生产得到氢气、一氧化碳、氮气。本申请通过在较低压力下分离原料气,有效降低能耗,通过准确控制燃料气中的二氧化碳与水实现兰炭炉燃烧室火焰长度控制与温度分布均匀,本申请能够有效减少气体废弃物排放、降低资源消耗。(The invention discloses a method for producing hydrogen, carbon monoxide and nitrogen by a semi-coke furnace, which comprises the steps of separating semi-coke tail gas from liquid substances to obtain raw material gas, adsorbing and separating the raw material gas by adopting pressure swing adsorption with the working pressure of-0.05-0.1 MPa, and obtaining water, carbon dioxide, unsaturated hydrocarbons, phenolic gases and C at a low-pressure desorption end of an adsorption tower 2 + Methane isAnd (3) circulating gas, namely obtaining hydrogen, argon, oxygen, nitrogen and carbon monoxide as product gas at the high-pressure end of the adsorption tower, sending the circulating gas into a semi-coke combustion chamber as fuel, and sending oxygen-enriched air as a combustion improver to produce and obtain the hydrogen, the carbon monoxide and the nitrogen. This application is through separating the feed gas under lower pressure, effectively reduces the energy consumption, and carbon dioxide and water through the accurate control in the fuel gas realize that blue charcoal stove combustion chamber flame length control is even with temperature distribution, and this application can effectively reduce gaseous discarded object and discharge, reduce resource consumption.)

1. A method for producing hydrogen, carbon monoxide and nitrogen by a semi-coke furnace is characterized by comprising the following steps: separating semi-coke tail gas from liquid substances to obtain raw material gas, performing pressure swing adsorption at the working pressure of-0.05-0.1 MPa to separate the raw material gas, and obtaining water, carbon dioxide, unsaturated hydrocarbons, phenolic gases and C at the low-pressure desorption end of an adsorption tower₂ ⁺Methane is circulating gas, hydrogen, argon, oxygen, nitrogen and carbon monoxide are obtained from the high-pressure end of the adsorption tower as product gas, the circulating gas is sent into a semi-coke combustion chamber to be used as fuel, and meanwhile, oxygen-enriched air is sent into the semi-coke combustion chamber to be used as combustion improver, and hydrogen, carbon monoxide and nitrogen are obtained through production.

2. The semi-coke furnace hydrogen, carbon monoxide and nitrogen production method according to claim 1, characterized in that: the liquid substance separation comprises cooling, tar and benzene recovery and sulfide removal.

3. The semi-coke furnace hydrogen, carbon monoxide and nitrogen production method according to claim 1, characterized in that: the pressure swing adsorption uses a carbon molecular sieve as an adsorbent.

4. The semi-coke furnace hydrogen, carbon monoxide and nitrogen production method according to claim 1, characterized in that: the pressure swing adsorption uses a molecular sieve with high silica-alumina ratio of more than 10:1 as an adsorbent.

5. The semi-coke furnace hydrogen, carbon monoxide and nitrogen production method according to claim 1, characterized in that: the concentration sum of carbon dioxide and water in the combustion chamber is controlled to be 37-57%.

6. The semi-coke furnace hydrogen, carbon monoxide and nitrogen production method according to claim 1, characterized in that: the oxygen content in the oxygen-enriched air is 50-100%.

7. The semi-coke furnace hydrogen, carbon monoxide and nitrogen production method according to claim 1, characterized in that: the hydrogen, carbon monoxide and nitrogen obtained by the production can be used as chemical synthesis raw material gases.

Technical Field

The invention belongs to the field of metallurgy, energy conservation and environmental protection, and particularly relates to a method for producing hydrogen, nitrogen and carbon monoxide by a semi-coke furnace, which can effectively reduce the emission of gas wastes and reduce the resource consumption.

Background

CN108977244A of Zhangbao ball, a Chinese Tianchen engineering Co., Ltd, announces a method for preparing liquefied natural gas by using oxygen-enriched modified semi-coke tail gas. Firstly, carrying out oxygen-enriched modification on semi-coke tail gas by using oxygen-enriched gas, carrying out wet desulphurization and pressurization on the semi-coke tail gas, and then carrying out pre-purification to remove tar, naphthalene and benzene in the modified semi-coke tail gas; after relay pressurization, fine desulfurization is carried out in a transformation mode to carry out methanation reaction, and synthesis gas is obtained; and (3) sequentially decarbonizing the synthesis gas, drying and dehydrating, and carrying out cryogenic liquefaction to finally obtain the liquefied natural gas. The regenerated gas obtained by pre-purification and cryogenic liquefaction can be used as fuel gas for a boiler room after being mixed. After the semi-coke tail gas is subjected to rich oxidation modification, the content of nitrogen is reduced, and CH in the tail gas is improved₄，CO，CO₂The content of the components beneficial to the subsequent synthesis and methanation further reduces the energy consumption in the whole LNG production process, and has higher economic benefit. The energy is recycled in the preparation process, so that the exhaust emission can be reduced, the energy and heat of the device can be fully utilized, the energy is saved, the environment is protected, and the environmental benefit and the economic benefit are high.

He-Jutang CN103074133A discloses an external coal gas processing method in an internal heating coal carbonization process, which is based on a coal carbonization process taking CO2 as a combustion process temperature control component, wherein an oxidant used in the coal carbonization process is rich oxygen and CO₂Mixture of gases, the discharged gas consisting mainly of H₂、CO、CH₄、CO₂、H₂O and the likeThe coal gas is subjected to CO removal₂The process becomes the first decarbonization gas TT1Q, and the first decarbonization gas TT1Q is used for co-producing H₂And LNG, H₂Used in the process of coal tar hydrogenation, thereby forming internal heating type semi coke preparation, tar hydrogenation and coal gas H preparation₂And LNG combined processes. Because the process of preparing LNG is simultaneously used for purifying H₂The process has high economical efficiency, and is particularly suitable for the internal heating type carbonization semi coke preparation, tar hydrogenation and coal gas co-production of H₂And LNG. Carbon dioxide is a good idea for regulating the temperature of furnace gas, but the idea of carbon dioxide as an oxidant is difficult to implement.

CN101250419B of Zhajun, et al, Western' an building science and technology university announces a coal gas internal heat low-temperature carbonization method, in which oxygen-enriched or pure oxygen is combusted with coal gas in an external burner to generate high-temperature waste gas as a basic heat source required by coal carbonization; mixing the generated high-temperature waste gas with the cold coal gas generated in the dry distillation process after tar removal to prepare high-temperature circulating gas with the temperature of 680-810 ℃; and (3) blowing the high-temperature circulating gas into an internal heating type coal carbonization furnace, and heating the coal in the furnace in a non-oxidation or weak-oxidation manner to realize non-combustion circulation of circulating part of coal gas. The method can effectively reduce the nitrogen content in the coal gas, improve the heat value of the coal gas, improve the yield of tar and improve the quality of semi coke. However, the problems of uneven combustion and local sintering in the coal dry distillation process under the oxygen-rich condition are the biggest dilemma of the similar process at present, and the large-scale process of the semi-coke furnace is also greatly difficult.

According to the invention patent, the content of carbon dioxide and water in the fuel gas is consciously and accurately controlled to control the working temperature and the uniform temperature distribution of the combustion chamber, and attention is not paid to the invention.

The pressure swing adsorption gas separation technology is a common technology, but the separation of hydrogen, nitrogen and carbon monoxide from semi-coke tail gas is difficult to realize in a low-pressure environment of-0.05-0.1 MPa, the separation is realized under higher pressure in the common technology, the energy consumption cost is higher, and the inventor invents a special adsorbent to realize the low-pressure low-cost separation.

The oxygen enrichment is used as a combustion improver, the fuel with high calorific value is directly combusted, the temperature distribution of a combustion runner is easy to be uneven, even the sintering phenomenon occurs, the flame length control and the temperature distribution of a combustion chamber of the semi-coke furnace can be relatively uniform by accurately controlling carbon dioxide and water in the fuel gas, the method is discovered by an inventor after a long time of groping, and the mixed gas of hydrogen, carbon monoxide and nitrogen is obtained by the method.

Disclosure of Invention

The method for producing hydrogen, carbon monoxide and nitrogen by using the semi-coke furnace separates semi-coke tail gas into liquid substances (comprising the processes of cooling, recovering tar and benzene, removing sulfide and the like) and then calls the liquid substances as raw material gas. For the separation of high-concentration carbon dioxide from raw gas by adopting a common process and activated carbon and silica gel adsorbents, the energy consumption is huge and cannot be paid. The special adsorbent and the pressure swing adsorption separation raw material gas with the working pressure of-0.05-0.1 MPa are adopted, so that the operation energy consumption is greatly reduced. Two desorption gases are obtained at the low-pressure end of the adsorption tower, wherein one desorption gas is high-concentration water, carbon dioxide is called as first circulating gas, and the other desorption gas is carbon dioxide, unsaturated hydrocarbons, phenolic gases and C₂ ⁺Methane is called second circulating gas, hydrogen, argon, oxygen, nitrogen and carbon monoxide obtained at the high-pressure end of the adsorption tower are called product gas, part of the first circulating gas and all the second circulating gas are sent into a semi-coke combustion chamber to be used as fuel, 50-100% of oxygen-enriched air is sent into the semi-coke combustion chamber to be used as combustion improver, and the produced hydrogen, carbon monoxide and nitrogen are used as chemical raw material gas; in order to ensure that the flame length of the combustion chamber meets the uniform heating requirement of the semi-coke furnace, the concentration sum of carbon dioxide and water in the fuel gas is controlled to be 37-57%.

The oxygen-enriched air is used as a combustion improver, and high-calorific-value fuel is mixed with carbon dioxide and water vapor, so that the temperature distribution of a combustion runner is uniform, and the sintering phenomenon is avoided.

Detailed Description

The present invention is further illustrated by the following examples, which are not intended to be limiting in any way, and any modifications or alterations based on the teachings of the present invention are intended to fall within the scope of the present invention.

The invention relates to a method for producing hydrogen, carbon monoxide and nitrogen by a semi-coke furnace, which comprises the steps of separating semi-coke tail gas from liquid substances to obtain raw material gas, performing pressure swing adsorption separation on the raw material gas under the working pressure of-0.05-0.1 MPa, obtaining water, carbon dioxide, unsaturated hydrocarbons, phenolic gases, C2+ and methane at the low-pressure desorption end of an adsorption tower as circulating gas, obtaining hydrogen, argon, oxygen, nitrogen and carbon monoxide at the high-pressure end of the adsorption tower as product gas, sending the circulating gas into a semi-coke combustion chamber as fuel, and sending oxygen-enriched air as a combustion improver to produce hydrogen, carbon monoxide and nitrogen.

Further, the liquid substance separation comprises cooling, tar and benzene recovery and sulfide removal.

Further, the pressure swing adsorption uses a carbon molecular sieve as an adsorbent.

Furthermore, the pressure swing adsorption uses a molecular sieve with high silica-alumina ratio of more than 10:1 as an adsorbent.

Furthermore, the concentration sum of carbon dioxide and water in the combustion chamber is controlled to be 37-57%.

Further, the hydrogen, carbon monoxide and nitrogen obtained by the production can be used as chemical synthesis raw material gases.

Example 1: a single-hole semi-coke furnace annual capacity is 7.5 million tons, the total capacity is 60 million tons, a semi-coke production line is used for producing hydrogen, carbon monoxide and nitrogen, semi-coke tail gas is separated from liquid substances (including processes of cooling, tar and benzene recovery, sulfide removal and the like) and then is called as raw material gas, a high-silicon-aluminum ratio molecular sieve with a silicon-aluminum ratio of 10:1 is used as an adsorbent, and the raw material gas is separated by pressure swing adsorption at the working pressure of-0.05 MPa. High concentrated water is obtained at the low-pressure desorption end of the adsorption tower, carbon dioxide is used as first circulating gas, carbon dioxide, unsaturated hydrocarbons, phenol gas and C₂ ⁺Methane is called second circulating gas, hydrogen, argon, oxygen, nitrogen and carbon monoxide obtained at the high-pressure end of the adsorption tower are called product gas, 70% of the first circulating gas and all the second circulating gas are sent into a semi-coke combustion chamber to be used as fuel, 50% of oxygen-enriched air is sent into the semi-coke combustion chamber to be used as combustion improver, and the produced hydrogen, carbon monoxide and nitrogen are used for ammonia synthesis raw material gas; in order to ensure that the flame length of the combustion chamber meets the uniform heating requirement of the semi-coke furnace, the flame is heated in fuel gasThe sum of the concentrations of carbon dioxide and water in (3) was controlled to be 37%.

Example 2: a production line of single-hole semi-coke furnace with annual capacity of 8 million tons and total capacity of 64 million tons for producing hydrogen, carbon monoxide and nitrogen is characterized in that semi-coke tail gas is separated into liquid substances (including processes of cooling, tar and benzene recovery, sulfide removal and the like) and then called as raw material gas, a high-silicon-aluminum ratio molecular sieve with a silicon-aluminum ratio of 15:1 is used as an adsorbent, and the raw material gas is separated by pressure swing adsorption at working pressure of-0.05-0.10 MPa. High concentrated water is obtained at the low-pressure desorption end of the adsorption tower, carbon dioxide is used as first circulating gas, carbon dioxide, unsaturated hydrocarbons, phenol gas and C₂ ⁺Methane is called second circulating gas, hydrogen, argon, oxygen, nitrogen and carbon monoxide obtained at the high-pressure end of the adsorption tower are called product gas, 40% of the first circulating gas and all the second circulating gas are sent into a semi-coke combustion chamber to be used as fuel, 85% of oxygen-enriched air is sent into the semi-coke combustion chamber to be used as combustion improver, and the produced hydrogen, carbon monoxide and nitrogen are used for synthesizing raw material gas by methanol and ammonia; in order to ensure that the flame length of the combustion chamber meets the uniform heating requirement of the semi-coke furnace, the concentration sum of carbon dioxide and water in fuel gas is controlled to be 41 percent.

Example 3: a single-hole semi-coke furnace annual capacity is 10 ten thousand tons, the total capacity is 80 ten thousand tons, a semi-coke production line is used for producing hydrogen, carbon monoxide and nitrogen, semi-coke tail gas is separated into liquid substances (including processes of cooling, tar and benzene recovery, sulfide removal and the like) and then is called as raw material gas, a high-silicon-aluminum ratio molecular sieve with a silicon-aluminum ratio of 20:1 is used as an adsorbent, and the raw material gas is separated by pressure swing adsorption at the working pressure of-0.05-0.1 MPa. High concentrated water is obtained at the low-pressure desorption end of the adsorption tower, carbon dioxide is used as first circulating gas, carbon dioxide, unsaturated hydrocarbons, phenol gas and C₂ ⁺Methane is called second circulating gas, hydrogen, argon, oxygen, nitrogen and carbon monoxide obtained at the high-pressure end of the adsorption tower are called product gas, 30% of the first circulating gas and all the second circulating gas are sent into a semi-coke combustion chamber to be used as fuel, 50% of oxygen-enriched air is sent into the semi-coke combustion chamber to be used as combustion improver, and the produced hydrogen, carbon monoxide and nitrogen are used for synthesizing raw material gas by methanol and ammonia; in order to ensure that the flame length of the combustion chamber meets the uniform heating requirement of the semi-coke furnace, two in fuel gasThe sum of the concentrations of carbon oxide and water was controlled at 55%.

The invention has the advantages of small investment, land occupation saving and energy consumption saving when part of the semi-coke tail gas is directly used as fuel and part of the semi-coke tail gas is converted into organic matters for chemical production.