CN103524300B - Method for jointly producing methyl alcohol by using water gas and coke oven gas - Google Patents
Method for jointly producing methyl alcohol by using water gas and coke oven gas Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000571 coke Substances 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 28
- 239000007789 gas Substances 0.000 claims abstract description 221
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 230000023556 desulfurization Effects 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000446 fuel Substances 0.000 claims abstract description 15
- 239000012071 phase Substances 0.000 claims abstract description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011280 coal tar Substances 0.000 claims abstract description 9
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- DSMZRNNAYQIMOM-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe].[Mo] DSMZRNNAYQIMOM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims 3
- 238000010792 warming Methods 0.000 claims 2
- 238000010521 absorption reaction Methods 0.000 claims 1
- 235000011089 carbon dioxide Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 claims 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 29
- 238000003786 synthesis reaction Methods 0.000 abstract description 29
- 238000010926 purge Methods 0.000 abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 8
- 239000002737 fuel gas Substances 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000002485 combustion reaction Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 206010035148 Plague Diseases 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23K—FEEDING FUEL TO COMBUSTION APPARATUS
- F23K5/00—Feeding or distributing other fuel to combustion apparatus
- F23K5/002—Gaseous fuel
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Industrial Gases (AREA)
Abstract
水煤气与焦炉煤气共同生产甲醇的方法，本发明涉及甲醇的生产方法。本发明是要解决现有的焦炉煤气生产甲醇的过程中没有合适的燃料气替代弛放气做为预热炉的加热燃料的技术问题。本方法：将水煤气和焦炉气通入气柜，通入湿法脱硫塔粗脱硫，然后再经预脱硫塔、铁钼转化器、钴钼转化器、氧化铁脱硫器的连续精脱硫，接着将精脱硫后的混合气体分成两部分，其中第一部分混合气体通入预热炉内升温，然后进入转化炉转化，得到合成气；第二部分混合气体引入到预热炉的燃烧器内，点火燃烧作为预热炉的燃料；合成气送入合成塔，合成的甲醇冷却分离后液相经精馏后得到甲醇产品，分离后气相送至煤焦油加氢变压吸附装置，回收氢气。本法用于水煤气与焦炉煤气共同生产甲醇。
The invention relates to a method for jointly producing methanol with water gas and coke oven gas, and the invention relates to a method for producing methanol. The invention aims to solve the technical problem that there is no suitable fuel gas to replace the purge gas as the heating fuel of the preheating furnace in the existing coke oven gas production process of methanol. This method: pass water gas and coke oven gas into the gas cabinet, pass into the wet desulfurization tower for rough desulfurization, and then go through the continuous fine desulfurization of the pre-desulfurization tower, iron-molybdenum converter, cobalt-molybdenum converter, and iron oxide desulfurizer, and then The mixed gas after fine desulfurization is divided into two parts, the first part of the mixed gas is passed into the preheating furnace to raise the temperature, and then enters the reformer for conversion to obtain synthesis gas; the second part of the mixed gas is introduced into the burner of the preheating furnace and ignited Combustion is used as fuel for the preheating furnace; the synthesis gas is sent to the synthesis tower, and the synthesized methanol is cooled and separated, and the liquid phase is rectified to obtain the methanol product, and the separated gas phase is sent to the coal tar hydrogenation pressure swing adsorption device to recover hydrogen. This method is used for co-production of methanol with water gas and coke oven gas.
Description
技术领域technical field
本发明涉及甲醇的生产方法。The present invention relates to a method for the production of methanol.
背景技术Background technique
采用焦炉煤气生产甲醇的过程是：焦炉煤气通入气柜中，再经风机送入湿法脱硫塔粗脱硫；然后再经压缩机压缩后、经预脱硫塔、钴钼转化器、氧化铁脱硫器处理进行精脱硫，然后经预热炉预热、转化炉部分氧化、再加压后，进入合成塔合成甲醇、得到粗甲经冷却分离后，液相经精馏处理，得到甲醇产品，气相的85%返回至合成段进行循环利用，而余下的15%为弛放气，做为预热炉的加热介质通入预热炉燃烧放热，其工艺流程框图如附图1所示。在此焦炉煤气生产甲醇的过程中，弛放气作为预热炉的燃料来产生热量，由于弛放气中含氢80%以上，而氢气又是煤焦油加氢环节的重要原料，弛放气须全部供给煤焦油加氢装置才能保证煤焦油加氢的满负荷生产。目前弛放气既要供给煤焦油加氢装置，又要作为预热炉的燃料，两者难以兼顾成为困扰现有焦炉煤气生产甲醇的难点。The process of using coke oven gas to produce methanol is: the coke oven gas is passed into the gas cabinet, and then sent to the wet desulfurization tower for rough desulfurization through the fan; then compressed by the compressor, passed through the pre-desulfurization tower, cobalt-molybdenum converter, oxidation The iron desulfurizer is used for fine desulfurization, and then preheated by the preheating furnace, partially oxidized by the reformer, and repressurized, and then enters the synthesis tower to synthesize methanol, and the crude methanol is obtained. After cooling and separation, the liquid phase is rectified to obtain methanol products , 85% of the gas phase is returned to the synthesis section for recycling, while the remaining 15% is relaxation gas, which is used as the heating medium of the preheating furnace and passed into the preheating furnace to burn and release heat. The process flow diagram is shown in Figure 1 . In the process of producing methanol from coke oven gas, the purge gas is used as the fuel of the preheating furnace to generate heat. Since the purge gas contains more than 80% hydrogen, and hydrogen is an important raw material for the hydrogenation of coal tar, the purge gas All the gas must be supplied to the coal tar hydrogenation unit to ensure the full capacity production of coal tar hydrogenation. At present, the purge gas should not only be supplied to the coal tar hydrogenation unit, but also be used as the fuel for the preheating furnace. It is difficult to balance the two, which has become a difficulty that plagues the existing coke oven gas production of methanol.
发明内容Contents of the invention
本发明是要解决现有的焦炉煤气生产甲醇的过程中没有合适的燃料气替代弛放气做为预热炉的加热燃料的技术问题，而提供一种水煤气与焦炉煤气共同生产甲醇的方法。The present invention aims to solve the technical problem that there is no suitable fuel gas to replace the purge gas as the heating fuel of the preheating furnace in the process of producing methanol from coke oven gas, and provides a method for co-producing methanol with water gas and coke oven gas method.
本发明的一种水煤气与焦炉煤气共同生产甲醇的方法，具体按以下步骤进行：A kind of water gas of the present invention and coke oven gas co-produce the method for methyl alcohol, specifically carry out according to the following steps:
一、将水煤气发生炉产出的水煤气通入气柜中，与通入气柜的焦炉气在气柜内混合，得到混合气体，其中混合气体中水煤气的体积百分比为15%～30%；1. Pass the water gas produced by the water gas generator into the gas holder, and mix it with the coke oven gas passed into the gas holder in the gas holder to obtain a mixed gas, wherein the volume percentage of the water gas in the mixed gas is 15% to 30%;
二、将气柜中的混合气体经风机加压至表压为20～30KPa，进入湿法脱硫塔，与脱硫液贫液逆向接触，将混合气体中的硫化氢脱除到20mg/L以下；2. The mixed gas in the gas cabinet is pressurized by the fan to a gauge pressure of 20-30KPa, enters the wet desulfurization tower, and is in reverse contact with the desulfurized liquid lean liquid, and removes the hydrogen sulfide in the mixed gas to below 20mg/L;
三、将经步骤二处理的混合气体经压缩机加压到表压为2.2～2.8MPa，经预脱硫塔、铁钼转化器、钴钼转化器、氧化铁脱硫器的连续精脱硫，将混合气体的总硫含量脱至小于0.1ppm；3. Pressurize the mixed gas treated in step 2 to a gauge pressure of 2.2 to 2.8 MPa through a compressor, and undergo continuous fine desulfurization of the pre-desulfurization tower, iron-molybdenum converter, cobalt-molybdenum converter, and iron oxide desulfurizer. The total sulfur content of the gas is removed to less than 0.1ppm;
四、将经步骤三处理的混合气体分成两部分，其中第一部分混合气体通入预热炉；第二部分混合气体引入到预热炉的燃烧器内，点火燃烧作为预热炉的燃料；其中第一部分混合气体与第二部分混合气体的体积比为10～15：1，预热炉内混合气体升温至600～620℃，然后进入转化炉，将混合气体中的甲烷转化成一氧化碳和氢气，得到合成气；Four, the mixed gas processed in step 3 is divided into two parts, wherein the first part of the mixed gas is passed into the preheating furnace; the second part of the mixed gas is introduced into the burner of the preheating furnace, and ignited and burned as the fuel of the preheating furnace; The volume ratio of the first part of the mixed gas to the second part of the mixed gas is 10-15:1. The mixed gas in the preheating furnace is heated to 600-620°C, and then enters the reformer to convert the methane in the mixed gas into carbon monoxide and hydrogen. get synthesis gas;
五、步骤四得到的合成气经合成压缩机加压到表压为3.2～3.8MPa，送入合成塔，在合成甲醇触媒的作用下合成甲醇，合成塔出口气体温度控制在280～300℃，气体冷却分离后的液相为粗甲醇，粗甲醇再经过精馏后，得到甲醇产品；气体冷却分离后的气相的体积的85%返回至合成压缩机循环，气相的体积的15%送至煤焦油加氢变压吸附装置，回收得到氢气。5. The synthesis gas obtained in step 4 is pressurized to a gauge pressure of 3.2 to 3.8 MPa through a synthesis compressor, and sent to a synthesis tower to synthesize methanol under the action of a catalyst for methanol synthesis. The temperature of the outlet gas of the synthesis tower is controlled at 280 to 300°C. The liquid phase after gas cooling and separation is crude methanol, and the crude methanol is rectified to obtain methanol products; 85% of the volume of the gas phase after gas cooling and separation is returned to the synthetic compressor for circulation, and 15% of the volume of the gas phase is sent to the coal Tar hydrogenation pressure swing adsorption device, recovery of hydrogen.
本发明改变了常规的以富含80%氢气的弛放气做为预热炉做为燃料的做法，而是将廉价的水煤气应用到生产甲醇过程中，取部分水煤气与焦炉气的混合气做为预热炉燃料，而将甲醇合成塔的弛放气用来提取氢气，通过合理选择用于作为燃料气的混合气及作为合成气的混合气体的比例，使作为燃料气部分所释放的能力恰恰满足被加热气体的要求，使经济效益提高15%～40%，收到良好的效果。本发明的方法节约了保贵的富氢气源，收到了良好的效果，并且预热炉内的烧嘴不需要做任何改动，就可以直接采用焦炉煤气与水煤气混合燃料供预热炉使用。The present invention changes the conventional practice of using the purge gas rich in 80% hydrogen as the fuel for the preheating furnace, but applies cheap water gas to the methanol production process, and takes part of the mixed gas of water gas and coke oven gas As the fuel of the preheating furnace, the purge gas of the methanol synthesis tower is used to extract hydrogen, and the ratio of the mixed gas used as the fuel gas and the mixed gas used as the synthesis gas is reasonably selected to make the released part of the fuel gas The capacity just meets the requirements of the heated gas, which increases the economic benefit by 15% to 40%, and receives good results. The method of the present invention saves precious hydrogen-rich gas sources and achieves good results, and the burners in the preheating furnace can directly use the mixed fuel of coke oven gas and water gas for the preheating furnace without any modification.
本发明采用水煤气与焦炉气混合气体作为甲醇的生产原料，既保证了甲醇的生产质量和纯度，又能有效的控制生产成本。同时利用水煤气与焦炉气混合气体给预热炉升温，保证提供预热炉反应所需的足够热值，又能避免单独使用焦炉气或水煤气热值过高或过低，预热炉温度不达标的问题。The invention adopts the mixed gas of water gas and coke oven gas as the raw material for methanol production, which not only ensures the production quality and purity of methanol, but also effectively controls the production cost. At the same time, the mixed gas of water gas and coke oven gas is used to raise the temperature of the preheating furnace to ensure sufficient calorific value required for the reaction of the preheating furnace, and it can also avoid excessive or low calorific value of coke oven gas or water gas used alone. Substandard issues.
附图说明Description of drawings
图1是现有技术的工艺流程示意图；Fig. 1 is the technological process schematic diagram of prior art;
图2是具体实施方式一的工艺流程示意图。Fig. 2 is a schematic diagram of the process flow of Embodiment 1.
具体实施方式Detailed ways
具体实施方式一：本实施方式的一种水煤气与焦炉煤气共同生产甲醇的方法，具体按以下步骤进行：Specific implementation mode one: a kind of water gas and coke oven gas of the present embodiment co-produce the method for methanol, specifically carry out according to the following steps:
一、将水煤气发生炉产出的水煤气通入气柜中，与通入气柜的焦炉气在气柜内混合，得到混合气体，其中混合气体中水煤气的体积百分比为15%～30%；1. Pass the water gas produced by the water gas generator into the gas holder, and mix it with the coke oven gas passed into the gas holder in the gas holder to obtain a mixed gas, wherein the volume percentage of the water gas in the mixed gas is 15% to 30%;
二、将气柜中的混合气体经风机加压至表压为20～30KPa，进入湿法脱硫塔，与脱硫液贫液逆向接触，将混合气体中的硫化氢脱除到20mg/L以下；2. The mixed gas in the gas cabinet is pressurized by the fan to a gauge pressure of 20-30KPa, enters the wet desulfurization tower, and is in reverse contact with the desulfurized liquid lean liquid, and removes the hydrogen sulfide in the mixed gas to below 20mg/L;
三、将经步骤二处理的混合气体经压缩机加压到表压为2.2～2.8MPa，经预脱硫塔、铁钼转化器、钴钼转化器、氧化铁脱硫器的连续精脱硫，将混合气体的总硫含量脱至小于0.1ppm；3. Pressurize the mixed gas treated in step 2 to a gauge pressure of 2.2 to 2.8 MPa through a compressor, and undergo continuous fine desulfurization of the pre-desulfurization tower, iron-molybdenum converter, cobalt-molybdenum converter, and iron oxide desulfurizer. The total sulfur content of the gas is removed to less than 0.1ppm;
四、将经步骤三处理的混合气体分成两部分，其中第一部分混合气体通入预热炉；第二部分混合气体引入到预热炉的燃烧器内，点火燃烧作为预热炉的燃料；其中第一部分混合气体与第二部分混合气体的体积比为10～15：1，预热炉内混合气体升温至600～620℃，然后进入转化炉，将混合气体中的甲烷转化成一氧化碳和氢气，得到合成气；Four, the mixed gas processed in step 3 is divided into two parts, wherein the first part of the mixed gas is passed into the preheating furnace; the second part of the mixed gas is introduced into the burner of the preheating furnace, and ignited and burned as the fuel of the preheating furnace; The volume ratio of the first part of the mixed gas to the second part of the mixed gas is 10-15:1. The mixed gas in the preheating furnace is heated to 600-620°C, and then enters the reformer to convert the methane in the mixed gas into carbon monoxide and hydrogen. get synthesis gas;
五、步骤四得到的合成气经合成压缩机加压到表压为3.2～3.8MPa，送入合成塔，在合成甲醇触媒的作用下合成甲醇，合成塔出口气体温度控制在280～300℃，气体冷却分离后的液相为粗甲醇，粗甲醇再经过精馏后，得到甲醇产品；气体冷却分离后的气相的体积的85%返回至合成压缩机循环，气相的体积的15%送至煤焦油加氢变压吸附装置，回收得到氢气。5. The synthesis gas obtained in step 4 is pressurized to a gauge pressure of 3.2 to 3.8 MPa through a synthesis compressor, and sent to a synthesis tower to synthesize methanol under the action of a catalyst for methanol synthesis. The temperature of the outlet gas of the synthesis tower is controlled at 280 to 300°C. The liquid phase after gas cooling and separation is crude methanol, and the crude methanol is rectified to obtain methanol products; 85% of the volume of the gas phase after gas cooling and separation is returned to the synthetic compressor for circulation, and 15% of the volume of the gas phase is sent to the coal Tar hydrogenation pressure swing adsorption device, recovery of hydrogen.
具体实施方式二：本实施方式与具体实施方式一不同的是步骤一中水煤气的体积百分比组成为：一氧化碳为40%～50%、氢气为32～38%，二氧化碳16～20%，其余为杂质。其他与具体实施方式一相同。Specific embodiment 2: The difference between this embodiment and specific embodiment 1 is that the volume percentage of water gas in step 1 is composed of: carbon monoxide is 40% to 50%, hydrogen is 32 to 38%, carbon dioxide is 16 to 20%, and the rest is impurities . Others are the same as the first embodiment.
具体实施方式三：本实施方式与具体实施方式一或二不同的是步骤二中将气柜中的混合气体经风机加压至表压为25～28KPa。其他与具体实施方式一相同。Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is that in step 2, the mixed gas in the gas cabinet is pressurized to a gauge pressure of 25-28 KPa through a fan. Others are the same as the first embodiment.
具体实施方式四：本实施方式与具体实施方式一至三之一不同的是步骤二中的脱硫液为纯碱。其他与具体实施方式一至三之一相同。Embodiment 4: This embodiment differs from Embodiment 1 to Embodiment 3 in that the desulfurization liquid in step 2 is soda ash. Others are the same as one of the specific embodiments 1 to 3.
具体实施方式五：本实施方式与具体实施方式一至四之一不同的是步骤三中混合气体经压缩机加压到表压为2.5～2.7MPa。其他与具体实施方式一至四之一相同。Embodiment 5: This embodiment differs from Embodiments 1 to 4 in that in step 3, the mixed gas is pressurized by a compressor to a gauge pressure of 2.5-2.7 MPa. Others are the same as one of the specific embodiments 1 to 4.
具体实施方式六：本实施方式与具体实施方式一至五之一不同的是步骤三中混合气体的总硫含量脱至0.05ppm。其他与具体实施方式一至五之一相同。Embodiment 6: This embodiment differs from Embodiment 1 to Embodiment 5 in that the total sulfur content of the mixed gas in step 3 is reduced to 0.05 ppm. Others are the same as one of the specific embodiments 1 to 5.
具体实施方式七：本实施方式与具体实施方式一至六之一不同的是步骤四中第一部分混合气体与第二部分混合气体的体积比为12～13：1。其他与具体实施方式一至六之一相同。Embodiment 7: This embodiment differs from Embodiments 1 to 6 in that the volume ratio of the first part of the mixed gas to the second part of the mixed gas in step 4 is 12-13:1. Others are the same as one of the specific embodiments 1 to 6.
具体实施方式八：本实施方式与具体实施方式一至七之一不同的是步骤四中第一部分混合气体通入预热炉内升温至610～615℃。其他与具体实施方式一至七之一相同。Embodiment 8: This embodiment differs from Embodiments 1 to 7 in that in Step 4, the first part of the mixed gas is passed into the preheating furnace to raise the temperature to 610-615°C. Others are the same as one of the specific embodiments 1 to 7.
具体实施方式九：本实施方式与具体实施方式一至八之一不同的是步骤五中合成气加压到表压为3.4～3.6MPa。其他与具体实施方式一至八之一相同。Embodiment 9: This embodiment differs from Embodiment 1 to Embodiment 8 in that in Step 5, the synthesis gas is pressurized to a gauge pressure of 3.4-3.6 MPa. Others are the same as one of the specific embodiments 1 to 8.
具体实施方式十：本实施方式与具体实施方式一至九之一不同的是步骤五中合成塔出口温度控制在285～295℃。其他与具体实施方式一至九之一相同。Embodiment 10: This embodiment is different from Embodiment 1 to Embodiment 9 in that the outlet temperature of the synthesis tower in step 5 is controlled at 285-295°C. Others are the same as one of the specific embodiments 1 to 9.
具体实施方式十一：本实施方式与具体实施方式一至十之一不同的是步骤五中合成塔触媒为铜基催化剂。其他与具体实施方式一至十之一相同。Embodiment 11: This embodiment is different from Embodiments 1 to 11 in that the catalyst in the synthesis tower in step 5 is a copper-based catalyst. Others are the same as those in the first to tenth specific embodiments.
具体实施方式十二：本实施方式与具体实施方式一至十一之一不同的是步骤五中合成气的组成按体积百分比为60～65%的氢气、20～30%的一氧化碳和余量的杂质。其他与具体实施方式一至十一之一相同。Embodiment 12: This embodiment differs from Embodiments 1 to 11 in that the composition of the synthesis gas in step 5 is 60-65% hydrogen by volume, 20-30% carbon monoxide and the remaining impurities . Others are the same as one of the specific embodiments 1 to 11.
本实施方式中所述的杂质为甲烷和氮气。The impurities described in this embodiment are methane and nitrogen.
用以下试验验证本发明的有益效果：Verify beneficial effect of the present invention with following test:
试验1：本试验1的一种水煤气与焦炉煤气共同生产甲醇的方法，具体按以下步骤进行：Test 1: A kind of water gas and coke oven gas co-production method of methanol in this test 1, specifically according to the following steps:
一、将水煤气发生炉产出的水煤气通入气柜中，与通入气柜的焦炉气在气柜内混合，得到混合气体，其中混合气体中水煤气的体积百分比为25%；1. Pass the water gas produced by the water gas generator into the gas holder, and mix it with the coke oven gas passed into the gas holder in the gas holder to obtain a mixed gas, wherein the volume percentage of the water gas in the mixed gas is 25%;
其中水煤气的体积百分比组成为：一氧化碳为45%、氢气为35%，二氧化碳为18%，其余为杂质；Wherein the volume percentage of water gas is composed of: carbon monoxide is 45%, hydrogen is 35%, carbon dioxide is 18%, and the rest are impurities;
二、将气柜中的混合气体经风机加压至表压为20KPa，进入湿法脱硫塔，与脱硫液纯碱贫液逆向接触，将混合气体中的硫化氢脱除到9mg/L；2. Pressurize the mixed gas in the gas cabinet to a gauge pressure of 20KPa through the fan, enter the wet desulfurization tower, and contact it with the desulfurized soda ash lean liquid in reverse, and remove the hydrogen sulfide in the mixed gas to 9mg/L;
三、将经步骤二处理的混合气体经压缩机加压到表压为2.5MPa，经预脱硫塔、铁钼转化器、钴钼转化器、氧化铁脱硫器的连续精脱硫，将混合气体的总硫含量脱至0.08ppm；3. The mixed gas treated in step 2 is pressurized to a gauge pressure of 2.5MPa through the compressor, and the continuous fine desulfurization of the pre-desulfurization tower, iron-molybdenum converter, cobalt-molybdenum converter, and iron oxide desulfurizer, the mixed gas The total sulfur content is removed to 0.08ppm;
四、将经步骤三处理的混合气体分成两部分，其中第一部分混合气体通入预热炉；第二部分混合气体引入到预热炉的燃烧器内，点火燃烧作为预热炉的燃料；其中第一部分混合气体与第二部分混合气体的体积比为10：1，预热炉内混合气体升温至620℃，然后进入转化炉，将混合气体中的甲烷转化成一氧化碳和氢气，得到合成气，合成气中氢气的体积百分比为60%，一氧化炭为30%，氮气为5%，甲烷为5%；Four, the mixed gas processed in step 3 is divided into two parts, wherein the first part of the mixed gas is passed into the preheating furnace; the second part of the mixed gas is introduced into the burner of the preheating furnace, and ignited and burned as the fuel of the preheating furnace; The volume ratio of the first part of the mixed gas to the second part of the mixed gas is 10:1. The temperature of the mixed gas in the preheating furnace is raised to 620°C, and then enters the reformer to convert the methane in the mixed gas into carbon monoxide and hydrogen to obtain synthesis gas. The volume percentage of hydrogen in the syngas is 60%, carbon monoxide is 30%, nitrogen is 5%, and methane is 5%;
五、步骤四得到的合成气加压到3.5MPa，送入合成塔，在触媒铜基催化剂的作用下合成甲醇，合成塔出口气体温度控制在290℃，气体冷却分离后的液相为粗甲醇，粗甲醇再经过精馏后，得到甲醇产品；气体冷却分离后的气相的体积的85%返回至合成压缩机循环，气相的体积的15%送至煤焦油加氢变压吸附装置，回收得到氢气。5. The synthesis gas obtained in step 4 is pressurized to 3.5 MPa, and sent to the synthesis tower to synthesize methanol under the action of the catalyst copper-based catalyst. The temperature of the gas at the outlet of the synthesis tower is controlled at 290°C, and the liquid phase after gas cooling and separation is crude methanol After the crude methanol is rectified again, methanol product is obtained; 85% of the volume of the gas phase after gas cooling and separation is returned to the synthetic compressor for circulation, and 15% of the volume of the gas phase is sent to the coal tar hydrogenation pressure swing adsorption device, and recovered to obtain hydrogen.
本试验1改变了常规的以富含80%氢气的弛放气做为预热炉做为燃料的做法，而是将廉价的水煤气应用到生产甲醇过程中，取部分水煤气与焦炉气的混合气做为预热炉燃料，而将甲醇合成塔的弛放气用来提取氢气，通过合理选择用于作为燃料气的混合气及作为合成气的混合气体的比例，使作为燃料气部分所释放的能力恰恰满足被加热气体的要求，使经济效益提高30%，若按此计算，一年可多产出6千万左右的经济效益，相当可观，收到良好的效果。本试验的方法节约了保贵的富氢气源，收到了良好的效果，并且预热炉内的烧嘴不需要做任何改动，就可以直接采用焦炉煤气与水煤气混合燃料供预热炉使用，对原有的工艺设备基础上改动方便。This test 1 changed the conventional practice of using 80% hydrogen-rich purge gas as the fuel for the preheating furnace, but applied cheap water gas to the methanol production process, taking part of the mixture of water gas and coke oven gas Gas is used as fuel for the preheating furnace, and the purge gas from the methanol synthesis tower is used to extract hydrogen. By rationally selecting the ratio of the mixed gas used as fuel gas and the mixed gas used as synthesis gas, the part of the gas released as fuel gas The ability to meet the requirements of the heated gas can increase the economic benefit by 30%. According to this calculation, an additional economic benefit of about 60 million can be produced a year, which is quite considerable and has received good results. The method of this test saves the precious hydrogen-rich gas source, and has received good results, and the burner in the preheating furnace does not need to be changed in any way, and the mixed fuel of coke oven gas and water gas can be directly used for the preheating furnace. It is convenient to modify the original process equipment.
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