WO2012145910A1 - 生产甲醇的方法和设备 - Google Patents
生产甲醇的方法和设备 Download PDFInfo
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- WO2012145910A1 WO2012145910A1 PCT/CN2011/073445 CN2011073445W WO2012145910A1 WO 2012145910 A1 WO2012145910 A1 WO 2012145910A1 CN 2011073445 W CN2011073445 W CN 2011073445W WO 2012145910 A1 WO2012145910 A1 WO 2012145910A1
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- WIPO (PCT)
- Prior art keywords
- gas
- converter
- sterol
- converter gas
- coke oven
- Prior art date
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Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/06—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by mixing with gases
Definitions
- the present invention relates to the field of chemical engineering, and more particularly to a method and apparatus for producing sterols.
- the present invention provides a method and an apparatus for producing decyl alcohol, which fully utilizes carbon in converter gas by using converter gas generated during steelmaking and coke oven gas generated during coking process as raw materials.
- the elements and hydrogen in the coke oven gas save resources and improve economic efficiency.
- the present invention provides the following technical solutions:
- the invention discloses a method for producing sterols, comprising:
- the mixture is reacted to form a sterol.
- the process of purifying the converter gas comprises:
- the process of reacting with the mixed gas to form sterol comprises:
- the pure gas-catalyzed partial oxidation conversion process is used to convert the desulfurized mixture gas to obtain a synthesis gas; the synthesis gas is reacted at 215 ° C to 280 ° C and 5.5 Mpa to 6.5 Mpa to form sterol.
- the mixing process of the purified converter gas and the coke oven gas is performed by mixing the ratio of the purified converter gas and the coke oven gas according to the hydrogen to carbon ratio in the synthesis gas, and mixing the hydrogen in the synthesis gas.
- the carbon ratio by volume ratio (H 2 _C0 2 ) I (C0+C0 2 ) 2.0 ⁇ 2.05.
- the method before desulfurizing the mixed gas, the method further comprises: pressurizing the mixed gas to 2.2 Mpa ⁇
- the synthesis gas is reacted at 215 ° C to 280 ° C and 5.5 Mpa to 6.5 Mpa to form sterol.
- the syngas is reacted to form a sterol while water is used to replenish the lost water in the reaction, and the amount of the supplemented water and the sterol yield are 0.90 to 0.96:1 by weight.
- the method further comprises rectifying the sterol to obtain a sterol.
- the invention also discloses an apparatus for producing sterol, comprising:
- a converter gas purifying device connected to a converter gas exhaust port; a mixing device connected to the coke oven gas exhaust port and the exhaust port of the converter gas purifying device;
- a controller connected to the synthesizing device, the coke oven gas exhaust port, and the exhaust port of the converter gas purifying device.
- the synthesizing device comprises:
- a synthesis column connected to the exhaust port of the reforming unit.
- the method and equipment for producing sterol disclosed in the embodiment of the present invention can make the by-product gas converter gas generated in the steelmaking process pass through a purification process, thereby enabling it to be generated during the coking process.
- the coke oven gas is mixed in an appropriate ratio to generate a mixture after desulfurization and conversion.
- the hydrogen to carbon ratio in the syngas meets the theoretical value and improves production efficiency.
- converter gas and coke oven gas are both by-product gases in the industrial production process
- the addition of converter gas can improve the utilization rate of useful elements in the raw materials, and on the other hand, the industrial by-product gas can be used as raw materials to effectively reduce the exhaust gas.
- the emission reduces the pollution of the exhaust gas to the environment.
- the use of converter gas as exhaust gas in the steelmaking process as a raw material reduces production costs and improves economic efficiency.
- FIG. 1 is a flow chart of a process for producing decyl alcohol disclosed in an embodiment of the present invention.
- Embodiments of the present invention disclose a method and an apparatus for producing decyl alcohol, which are mixed with a coke oven gas generated in a coking process by using a by-product gas converter gas produced during a steelmaking process, in an appropriate ratio.
- a coke oven gas generated in a coking process by using a by-product gas converter gas produced during a steelmaking process, in an appropriate ratio.
- the embodiment of the invention discloses a method for producing sterol, which comprises: Purifying converter gas;
- the mixture is reacted to form a sterol.
- the converter gas is a mixed gas containing carbon monoxide and a small amount of carbon dioxide generated by the carbon in the molten iron at a high temperature and the blown oxygen during the converter steel making process.
- the recovered top-blown oxygen converter gas contains 60% to 80% carbon monoxide, 15% to 20% carbon dioxide, and nitrogen, hydrogen, trace oxygen and impurities such as sulfur, phosphorus, arsenic and fluorine. In the smelting process, the amount of converter gas is not balanced and the composition changes.
- the normal converter gas is only used for fuel purification.
- the purification process uses electric dust removal or water dust removal. It only removes the dust in the converter gas, so that the dust content is ⁇ 20mg/Nm 3 . It is a coarse purification and cannot remove the sulfur.
- impurities such as phosphorus, arsenic and fluorine. Since impurities such as sulfur, phosphorus, arsenic, and fluorine in the converter gas are harmful to the catalyst in the production process of decyl alcohol, it is necessary to remove these impurities before they can be used as a raw material for producing sterol.
- the embodiment of the invention adopts the method of wet dust removal and temperature reduction, that is, water dust removal, firstly purifies the converter gas, and then uses the temperature-temperature adsorption purification technology to remove impurities such as sulfur, phosphorus, arsenic and fluorine in the converter gas, and purifies and removes the impurity.
- the converter gas enters the blower at a flow rate of about 3000 Nm 3 /h and a pressure of lOkpa, and pressurizes the converter gas to about 45 ⁇ 55 kPa, preferably 50 kpa at the blower;
- the pressurized converter gas is passed through a gas-liquid separator to remove the water therein, and the water remaining in the converter gas after the water is removed by the water;
- the converter gas after adsorbing the impurities is subjected to arsenic removal by a refining unit composed of an arsenic removal unit to obtain a purified converter gas.
- a refining unit composed of an arsenic removal unit to obtain a purified converter gas.
- the arsenic removal agent in the process is used once.
- the process of adsorbing impurities in the converter gas in the present embodiment is sucked by three adsorbers.
- Impurities such as AsH 3 and HF.
- the specific method is that the converter gas passes through only one adsorber at the same time.
- the converter gas is passed to another adsorber after regeneration of the adsorbent to carry out impurities. Adsorption, so recycled.
- the adsorption purification unit since the impurity components adsorbed on the adsorbent are resolved by heating, each adsorber is at a different time. Then, the steps of adsorbing impurities by adsorption, heating and rinsing, and cold blowing are sequentially performed.
- a superheated steam hot-blowing adsorbent of about 350 ° C and 0.2 MPa generated by electric heater heating is used, and then the generated exhaust gas is cooled to separate waste water and exhaust gas, and the waste water is discharged through the sewage pipe network.
- the exhaust gas is vented by the torch; after flushing the adsorbent, the adsorbent is cold-blown by circulating nitrogen gas, and dried to cool to normal temperature.
- This process is an adsorption regeneration process, and the adsorbent can adsorb impurities in the converter gas after regeneration. Time looping.
- the purified converter gas and coke oven gas are mixed according to a certain ratio to obtain a mixed gas.
- the function of adding the converter gas to the coke oven gas is to adjust the hydrogen to carbon ratio of the synthesis gas to make it the most sterol. Good ratio.
- the hydrogen-carbon ratio is too low, that is, too much converter gas is added, which will cause problems such as catalyst carbonation and aging failure when synthesizing sterols; the hydrogen-carbon ratio is too high, that is, the converter gas is too small, although the synthesis can be reduced.
- the decane content in the gas prevents the catalyst from carbonizing, but increases the resistance when the hydrazine is formed from the syngas, increases the energy consumption, and reduces the production capacity of the equipment, resulting in a low sterol synthesis rate. Therefore, the mixing ratio of converter gas and coke oven gas must be strictly controlled.
- the mixing ratio of the converter gas and the coke oven gas after purification needs to be adjusted in real time, and the manner of adjusting the mixing ratio can be controlled by real-time monitoring.
- the mixing ratio of the converter gas and the coke oven gas after purification is adjusted in real time.
- the former is preferred in the present invention, but the choice of the mixing ratio adjustment mode does not affect the scope of protection of the present invention.
- the process of using the mixed gas to react to form sterol in this embodiment includes:
- the mixed gas is pressurized to 2.2 MPa to 2.8 MPa, and the applied pressure is preferably 2.5 MPa.
- a centrifugal turbine compressor or a reciprocating compressor may be used, and other technical persons may be used.
- the gas mixture after the pressurization is subjected to the straightening, and the total sulfur in the mixed gas is removed to 0. lppm or less, and there are various ways of removing the specific gas.
- the activated carbon can be used to remove the tar and the like in the coke oven gas, because the coke oven
- the form of sulfur in the gas is relatively complicated, and it is required to undergo two hydro-conversions to convert the organic sulfur of each form into inorganic sulfur, and then remove the inorganic to the total of ⁇ 0. lPPm by medium temperature oxidation and normal temperature oxidation.
- the physical absorption method removes most of the sulfides in the mixture, and then uses the dry fine desulfurizer such as hydrolysis and iron oxide, oxidation or activated carbon to remove trace sulfur compounds which may remain to meet the requirements of sterol synthesis.
- the solvent may be selected from a combination of decyl alcohol, sulfolane and diisopropanolamine, polyethylene glycol dioxime ether or propylene carbonate.
- the first mode is selected in the embodiment, but other methods and other substances known to those skilled in the art may be used in the method of removing the method;
- the pure gas-catalyzed partial oxidation conversion process is used to convert the desulfurized mixed gas to obtain a synthesis gas, which is converted from decane and a small amount of multi-carbon hydrocarbons in the mixed gas, including carbon monoxide, carbon dioxide and hydrogen.
- the reaction temperature of the synthesis gas is preferably 230 ° C to 260 ° C, more preferably 240 ° C ⁇
- the reaction pressure of the synthesis gas at 250 ° C is preferably 5.8 MPa to 6.2 MPa, more preferably 6.0 MPa.
- the concentration of CO and co 2 increases after the addition of converter gas, and the temperature of the synthesis tower will rise rapidly, exceeding the optimal operating temperature range of the synthesis catalyst. If long-term high temperature operation accelerates the catalyst crystal The grain growth, the surface area is reduced, thereby accelerating the aging of the catalyst, so the bed temperature must be lower than 280 ° C, and since the bed temperature is lower than 215 ° C, the catalyst may have a waxing reaction, so the optimum temperature range is 215 °. C ⁇ 280 ° C.
- the sterol synthesis tower of this embodiment is a shell-and-tube synthesis tower, and 1 ton of sterol will be added according to the calculation. Approximately 0.93 tons of steam is produced.
- the synthesis gas is reacted to form a decyl alcohol while replenishing the water lost in the reaction, that is, the shell boiler water by-product steam of the synthesis tower.
- the amount of the boiler water to be taken away is preferably 0.90 to 0.96:1, more preferably 0.93:1 by weight, and the amount of makeup water is about 3.15 t/h.
- the sterol formed by the reaction of the synthesis gas is crude sterol. Therefore, in the present embodiment, the sterol is rectified by a three-column distillation technique consisting of a pre-rectification column, a pressure column and an atmospheric column. The refined alcohol is obtained, and then the refined alcohol is sent to the finished tank area for storage.
- the method for producing sterol disclosed in the embodiments of the present invention uses a by-product gas converter gas which is originally used as an exhaust gas in steelmaking production as a raw material for producing sterol, and has a high CO content in the composition, and CO is also a valuable Chemical raw materials, as exhaust gas emissions, pollute the environment and waste resources. Therefore, according to the fact that there are many hydrogen elements in the coke oven gas and less carbon, and there are many carbon elements in the converter gas and less hydrogen, the two gases are mixed in a certain ratio and used as a raw material for producing sterol, which solves the problem of simply using coke.
- the gas consumption caused by the furnace gas as raw material is incomplete, the synthesis rate of sterol is low, the problem of waste of resources, and the environmental pollution is reduced. From the economic point of view, the use of waste gas as an industrial raw material also reduces the production cost.
- the invention also provides an apparatus for producing sterol, see Fig. 1, comprising:
- Converter gas purification device connected to the converter gas exhaust port 1;
- the mixing device 2 connected to the coke oven gas exhaust port and the exhaust port of the converter gas purification device 1 is the coke oven gas pipe in the present embodiment, and an opening is provided in the coke oven gas pipe.
- the purified converter gas, the coke oven gas is mixed with the purified converter gas to obtain a mixed gas;
- the mixed gas compressor 3 connected to the mixing device 1 , the mixed gas compressor 3 pressurizes the mixed gas to .2Mpa ⁇ 2.8Mpa;
- the reforming device 5 connected to the exhaust port of the stripping device 4, the mixture gas removed in the reforming device 5 is converted into a syngas comprising carbon monoxide and hydrogen, the ratio of hydrogen to carbon in the syngas is by volume ratio (H - C0 2 ) / (C0+C0 2 ) 2.0 - 2.05;
- a shell-and-tube synthesis tower 7 connected to the exhaust port of the synthesis gas compressor 6, and syngas is reacted in the synthesis tower 7 to form a sterol;
- the desulfurization device 4, the reforming device 5, the syngas compressor 6, and the synthesis column 7 in the present embodiment are collectively referred to as a synthesizing device that generates a sterol by a mixed gas reaction.
- a pre-rectification column 8 which are connected to the synthesis column 7 to rectify the sterol produced in the synthesis column 7 are also included.
- the mixing of the purified converter gas and the coke oven gas can be in the coke oven gas pipeline or in the mixed gas compressor, or other mixing devices can be provided, but the selection of the mixing device does not affect the present.
- the scope of protection of the invention can be in the coke oven gas pipeline or in the mixed gas compressor, or other mixing devices can be provided, but the selection of the mixing device does not affect the present. The scope of protection of the invention.
- the converter gas from the steelmaking process passes through the water dedusting device, the blower, the gas-liquid separator, the adsorption purification unit, and the refining unit in the converter gas purification device 1, and then cools the converter gas, removes the dust therein, and synthesizes and converts
- the catalyst is harmful to sulfur, phosphorus, arsenic, fluorine and other impurities, and the purified converter gas that meets the reaction requirements is obtained.
- the standard of the purified converter gas is: P3 ⁇ 4 ⁇ lPPm;C0S ⁇ lPPm;HF ⁇ 0.lPPm; AsH 3 ⁇ 5PPb H 2 S ⁇ lPPm, the converter gas from the converter is treated to reach the above standard, and then mixed with coke oven gas from the coke oven to obtain a mixed gas.
- the coke oven gas is pretreated in a coking plant prior to mixing with the purified converter gas.
- the pretreatment process is:
- the coke oven gas is provided with an electric tar catcher after the blower to remove the tar in the coke oven gas to below 50 mg/Nm 3 ;
- the ammonia in the coke oven gas is removed to 50 mg/Nm 3 or less by the pickling method in the ammonium sulfate section after the blower;
- the benzene in the coke oven gas is reduced to 2 g/Nm 3 or less;
- the hydrogen sulfide and hydrogen cyanide in the coke oven gas are reduced to 20 mg/Nm 3 or less by the PDS method. After mixing and compressing to 2.2Mpa ⁇ 2.8Mpa, enter the straightening device 4 to perform fine desulfurization of the mixture.
- the total sulfur is desorbed to below 0.1 ppm, and the desulfurized gas is mixed with oxygen from the outside, and converted into a conversion device 5 by a pure oxygen catalytic partial oxidation process to convert decane and a small amount of polycarbon hydrocarbons in the mixed gas into
- the useful components of the synthesis of sterol are carbon monoxide, carbon dioxide and hydrogen, that is, the synthesis gas required for the production of decyl alcohol, and then the synthesis gas is pressurized to 5.5 MPa to 6.5 MPa by the synthesis gas compressor 6, and the pressurized synthesis gas is in the synthesis tower.
- the reaction in 7 produces crude sterol, and the reaction temperature is controlled to be in the range of 215 ° C to 280 ° C by adding a certain amount of boiler water to the synthesis tower, and then the crude sterol is rectified by the three-column distillation technique to obtain refined sulphur. alcohol.
- the mixing ratio of the purified converter gas and the coke oven gas is controlled by real-time monitoring of the hydrogen-carbon ratio in the syngas, and adjusting the flow rates of the converter gas and the coke oven gas in real time according to the change of the hydrogen-carbon ratio.
- the gas which is not completely reacted in the synthesis tower 7 has multiple ways, for example, it is returned to the synthesis gas compressor 6 as a recycle gas, and the reaction is repeated after repeated compression, or is returned to the reforming device 5 as a heat source of the preheating furnace or the heating furnace.
- the utility model can also be utilized as a heat source for heating the coke oven, or extracting hydrogen in the purge gas as a hydrogen source, that is, the hydrogen is extracted by the pressure swing adsorption device, and the specific measures are known to those skilled in the art. It will not be described here, but the treatment of the gas which is not completely reacted in the synthesis tower does not affect the protection scope of the embodiment of the present invention.
- RSH+H 2 H 2 S+RH
- RSR+2H 2 H 2 S+2RH
- H 2 S+FeO FeS+H 2 0;
- ketone RSH, ketone RSR, R r SR 2 and CS 2 are all impurities in coke oven gas.
- the main reaction of the pure oxygen catalytic partial oxidation process carried out in the reforming unit 5 is as follows:
- the co, co 2 and 3 ⁇ 4 formed after the reaction are the main components of the syngas, and the hydrogen to carbon ratio in the syngas is controlled to be 2.0 to 2.05.
- the coke oven gas and converter gas produced by the steel coke production enterprise are used as raw materials.
- the composition of the raw materials is:
- the content of each component in coke oven gas is:
- the content of each component in the converter gas is:
- composition and impurities of the converter gas before and after purification are:
- the additional carbon source needs to be converter gas.
- the useful components after converter gas purification are: CO It is 63.22%; C0 2 is 13.30%; 3 ⁇ 4 is 3.50%, the purified converter gas temperature is controlled below 40 °C, and the pressure is below O.OlMpa.
- the flow rate of syngas at a certain time is 30000Nm 3 /h. According to the reasonable hydrogen-carbon ratio requirement, the value of F is 2.02, and the converter gas volume is XNmVh.
- the calculation formula is:
- the gas volume of the converter gas required at this time can be calculated to be 2288 Nm 3 /h.
- the syngas composition and hydrogen-carbon ratio before and after the converter gas are:
- the optimal inlet amount of the converter gas is adjusted at any time, and the sterol synthesis gas formed by the conversion of the mixed gas is pressurized to 6.0 MPa by the syngas compressor, and then the sterol synthesis column is introduced to obtain the crude sterol.
- the sterol synthesis adopts 6.0MPa low pressure synthesis technology, the synthesis tower adopts shell-and-tube type, and the obtained crude decyl alcohol is prepared by using pre-rectification tower, pressure tower and atmospheric tower three-column distillation technology to prepare refined sterol.
- the alcohol is sent to the finished tank area for storage. After testing, the quality of the sterol product produced by this process reaches the level of GB338-2004 superior product.
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Description
生产曱醇的方法和设备
技术领域 本发明涉及化工领域, 更具体地说, 涉及一种生产曱醇的方法和设备。
背景技术 目前生产曱醇的原料较多, 如天然气、 焦炉气、 石脑油、 重油、 煤或焦炭 等,在大多钢焦联产企业中利用炼焦过程中产生的焦炉煤气生产曱醇, 由于焦 炉煤气是高含氢的气体,使得在生产曱醇过程中,对原料焦炉煤气处理后产生 的合成气中的氢碳比远远偏离理论值 (按体积比氢碳比理论值 F= ( H -C02) I (C0+C02) =2.0 - 2.05 ), 导致合成气中的氢气不能得到充分的利用, 而最终被燃烧或放散,由于有用元素不能得到充分的利用,造成了资源的浪费, 同时生产曱醇的效率也较^^
发明内容 有鉴于此, 本发明提供一种生产曱醇的方法和设备,通过以炼钢过程中产 生的转炉煤气和炼焦过程中产生的焦炉煤气为原料,充分的利用了转炉煤气中 的碳元素和焦炉煤气中的氢元素, 节约了资源, 提高了经济效益。
为实现上述目的, 本发明提供了如下技术方案:
本发明公开了一种生产曱醇的方法, 包括:
净化转炉煤气;
将净化后的转炉煤气与焦炉煤气混合, 得到混合气;
利用所述混合气反应生成曱醇。
优选的, 净化转炉煤气的过程包括:
对转炉煤气加压;
除去加压后的转炉煤气中的机械水;
吸附除去机^ ^水后的转炉煤气中的杂质;
对吸附杂质后的转炉煤气进行脱砷, 得到净化后的转炉煤气。 优选的, 利用所述混合气反应生成曱醇的过程包括:
对所述混合气进行脱
采用纯氧催化部分氧化转化工艺转化脱硫后的混合气, 得到合成气; 利用所述合成气在 215 °C ~ 280°C , 5.5Mpa ~ 6.5 Mpa条件下反应生成曱 醇。
优选的, 净化后的转炉煤气与焦炉煤气的混合过程为,根据所述合成气中 的氢碳比调整净化后的转炉煤气与焦炉煤气的混合比例后进行混合,所述合成 气中氢碳比按体积比 ( H2_C02) I (C0+C02) =2.0 ~ 2.05。
优选的,对所述混合气进行脱硫前还包括:将所述混合气加压至 2.2Mpa ~
2.8Mpa。
优选的, 利用所述合成气在 215 °C ~ 280°C , 5.5Mpa ~ 6.5 Mpa条件下反应 生成曱醇。
优选的, 利用所述合成气反应生成曱醇同时用水补充反应中失去的水分, 所述补充的水的量与曱醇产量按重量比 0.90 ~ 0.96: 1。
优选的, 还包括对所述曱醇进行精馏, 得到精曱醇。
本发明还公开了一种生产曱醇的设备, 包括:
与转炉煤气排气口相连的转炉煤气净化装置;与焦炉煤气排气口和所述转 炉煤气净化装置排气口相连的混合装置;
与所述混合装置排气口相连的合成装置;
与所述合成装置、焦炉煤气排气口和所述转炉煤气净化装置排气口相连的 控制器。
优选的, 所述合成装置包括:
与所述混合装置排气口相连的脱硫装置;
与所述脱硫装置排气口相连的转化装置;
与所述转化装置排气口相连的合成塔。
从上述的技术方案可以看出, 本发明实施例公开的生产曱醇的方法和设 备,通过将炼钢过程中产生的副产气转炉煤气经过净化过程后,使其能够与炼 焦过程中产生的焦炉煤气按照适当的比例混合,使混合气经脱硫和转化后生成
的合成气中的氢碳比满足理论值的要求,提高了生产效率。 由于转炉煤气中的 碳元素含量较高, 而焦炉煤气中的氢元素含量较高,通过加入一定比例的转炉 煤气可以调节合成气中的氢碳比,转炉煤气和焦炉煤气的混合比例根据实时监 测的合成气中的氢碳比的变化而实时的进行调节,调节后的混合比例使合成气 中的氢碳比满足 = ( H -C02) / (C0+C02) =2.0 - 2.05的要求。
由于转炉煤气和焦炉煤气都是工业生产过程中的副产气,转炉煤气的加入 一方面可以提高原料中有用元素的利用率, 另一方面利用工业副产气做原料, 有效的减少了废气的排放, 减少了废气对环境的污染。 另外, 利用炼钢过程中 作为废气排放的转炉煤气做原料, 降低了生产成本, 提高了经济效益。
附图说明 为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施 例或现有技术描述中所需要使用的附图作筒单地介绍,显而易见地, 下面描述 中的附图仅仅是本发明的一些实施例, 对于本领域普通技术人员来讲,在不付 出创造性劳动的前提下, 还可以根据这些附图获得其他的附图。
图 1为本发明实施例公开的一种生产曱醇的工艺流程图。
具体实施方式 本发明实施例公开了一种生产曱醇的方法和设备,通过利用炼钢过程中产 生的副产气转炉煤气净化后,与炼焦过程中产生的焦炉煤气按照适当的比例混 合, 以使得混合气经脱硫和转化后生成的合成气中的氢碳比满足理论值的要 求,在利用合成气生产曱醇时,提高了原料中有用元素的利用率,节约了能源, 同时也减少了污染。
为了进一步了解本发明,下面结合附图和实施例对本发明优选实施方案进 行清楚、 完整地描述, 但是应当理解, 这些描述只是为进一步说明本发明的特 征和优点, 而不是对本发明权利要求的限制。
本发明实施例公开了一种生产曱醇的方法, 包括:
净化转炉煤气;
将净化后的转炉煤气与焦炉煤气混合, 得到混合气;
利用所述混合气反应生成曱醇。
转炉煤气为转炉炼钢过程中,由铁水中的碳在高温下和吹入的氧生成的包 含一氧化碳和少量二氧化碳的混合气体。 回收的顶吹氧转炉煤气含一氧化碳 60% ~ 80%, 二氧化碳 15% ~ 20%, 以及氮、 氢、 微量氧及硫、 磷、 砷、 氟等 杂质。 在冶炼过程, 转炉煤气的发生量中并不均衡, 成分也有变化。 通常的转 炉煤气净化后仅做燃料用, 净化过程采用电除尘或水除尘, 只是除去转炉煤气 中的粉尘, 使其粉尘含量≤20mg/Nm3即可, 属于粗净化, 不能除去其中的硫、 磷、 砷、 氟等微量杂质。 由于转炉煤气中的硫、 磷、 砷、 氟等杂质对曱醇生产 过程中的催化剂有害, 因此必须除去这些杂质后才能用作生产曱醇的原料。
转炉煤气由炉口喷出时, 温度高达 1450°C ~ 1500°C,并夹带大量氧化铁粉 尘, 需经降温、 除尘, 方能使用, 净化有湿法和干法两种类型。 本发明实施例 采用湿法除尘降温的方法, 即水除尘, 先对转炉煤气进行粗净化, 之后采用变 温吸附净化技术除去转炉煤气中的硫、 磷、 砷、 氟等杂质, 净化除杂过程具体 包括:
转炉煤气以约为 3000Nm3/h的流量、 lOkpa的压力进入鼓风机, 在鼓风机 处对转炉煤气加压至约 45 ~ 55kpa, 优选为 50 kpa;
将加压后的转炉煤气经过气液分离器, 除去其中的机^ ^水, 这些机^ ^水来 自水除尘后残留在转炉煤气中的水份;
吸附除去机^ ^水后的转炉煤气中的杂质;
吸附杂质后的转炉煤气经过由一台脱砷器组成的精制单元进行脱砷,得到 净化后的转炉煤气, 优选的, 此过程中的脱砷剂为一次性使用。
优选的,本实施例中吸附转炉煤气中杂质的过程在由 3台吸附器组成的吸
AsH3、 HF等杂质。 具体方式为转炉煤气在同一时间只经过一台吸附器, 当一 台吸附器中的吸附剂吸附的杂质接近饱和时,再将转炉煤气通入另一台吸附剂 再生之后的吸附器进行杂质的吸附, 如此循环使用。 吸附净化单元中, 由于吸 附在吸附剂上的杂质组份经加热便会解析出来,因此每台吸附器在不同的时间
便会依次经历由吸附剂吸附杂质、 加热沖洗、 冷吹等步骤。 优选的, 本实施例 中采用经电加热器加热产生的约为 350°C、 0.2Mpa的过热蒸汽热吹吸附剂,之 后将产生的废气冷却后分离出废水和废气,废水通过污水管网排出,废气经火 炬放空; 沖洗吸附剂之后, 采用循环使用的氮气对吸附剂进行冷吹, 使其干燥 降温至常温, 此过程为吸附的再生过程, 吸附剂再生后能够在吸附转炉煤气中 的杂质时循环使用。
经过净化后的转炉煤气与焦炉煤气按照一定比例进行混合, 得到混合气, 由于将转炉煤气配加到焦炉煤气中的作用是调节合成气的氢碳比,使其达到生 产曱醇的最佳比例。 氢碳比过低, 即转炉煤气配加量过多, 会造成合成曱醇时 的催化剂结碳、 老化失效等问题; 氢碳比过高, 即转炉煤气配加量过少, 虽然 可以降低合成气中的曱烷含量, 防止催化剂结碳,但是会使由合成气生成曱醇 时的阻力增大, 增加能耗, 降低设备的生产能力, 导致曱醇合成率低。 因此, 必须严格控制转炉煤气和焦炉煤气的混合比例。
本实施例中转炉煤气和焦炉煤气混合比例是通过实时监测合成气中的氢 碳比而实时调整的,所述合成气中氢碳比按体积比 F=( H -C02) I (C0+C02) =2.0 ~ 2.05 , 因此, 优选的, 所述净化后的转炉煤气与焦炉煤气按体积比净化后转炉 煤气: 焦炉煤气 =0.8 ~ 1.2: 9.2 ~ 8.8进行混合, 更优选的, 所述净化后的转炉 煤气与焦炉煤气按体积比净化后转炉煤气: 焦炉煤气 =0.95 ~ 1.05: 9.05 - 8.95 进行混合。
需要说明的是, 由于转炉煤气与焦炉煤气中的成分是实时变化的, 净化后 的转炉煤气与焦炉煤气的混合比例需要实时调整, 调整混合比例的方式可以 为,通过实时监测净化后的转炉煤气与焦炉煤气的成分, 结合合成气中的氢碳 比的监测结果, 实时的调整净化后的转炉煤气与焦炉煤气的混合比例; 也可以 采用生产过程中得到的净化后的转炉煤气与焦炉煤气成分的经验值,结合合成 气中的氢碳比的监测结果,实时的调整净化后的转炉煤气与焦炉煤气的混合比 例。 本发明优选前者, 但混合比例调整方式的选择不影响本发明的保护范围。 本实施例中利用所述混合气反应生成曱醇的过程包括:
将所述混合气加压至 2.2Mpa ~ 2.8Mpa, 所加压力优选为 2.5 Mpa,对混合 气体加压时可采用离心透平压缩机或往复式压缩机,也可为其他本领域技术人
员所公知的技术;
对加压后的混合气进行脱直, 将混合气中的总硫脱至 0. lppm以下, 具体 脱^ 方式有多种, 可采用活性炭脱除焦炉煤气中的焦油等物质, 由于焦炉煤气 中硫的形态比较复杂, 需经两次加氢转化, 将各形态的有机硫转化成无机硫, 再通过中温氧化辞和常温氧化辞脱除无机 至总 <0. lPPm; 也可采用溶剂物 理吸收法脱除混合气中的大部分硫化物,再采用水解和氧化铁、氧化辞或活性 炭等干法精脱硫剂脱除可能残留的痕量硫化物, 以达到曱醇合成的要求, 采用 溶剂物理吸收法时, 溶剂可选用曱醇、 环丁砜和二异丙醇胺组合溶液、 聚乙二 醇二曱醚或碳酸丙烯酯。本实施例中选用第一种方式,但脱^ 方式还可以采用 本领域技术人员公知的其他方法和其他物质;
采用纯氧催化部分氧化转化工艺转化脱硫后的混合气,得到合成气, 所述 合成气由混合气中的曱烷及少量多碳烃转换而来, 包括一氧化碳、二氧化碳和 氢气,所述合成气中氢碳比按体积比 F=( H2_C02) / (C0+C02) =2.0 ~ 2.05 ,优选的, 所述合成气中氢碳比按体积比 F= ( H -C02) I (C0+C02) =2.01 ~ 2.03 , 更优选的, 所述合成气中氢碳比按体积比 F= ( H -C02) I (C0+C02) =2.02;
之后, 利用所述合成气在 215 °C ~ 280°C , 5.5Mpa ~ 6.5 Mpa条件下反应生 成曱醇, 合成气的反应温度优选为 230°C ~ 260°C , 更优选为 240°C ~ 250°C , 合成气的反应压力优选为 5.8Mpa ~ 6.2 Mpa, 更优选为 6.0Mpa。
由于曱醇合成反应是强烈的放热反应, 加入转炉煤气后, CO和 co2浓度 增大, 合成塔温度将迅速上涨, 超过合成催化剂的最佳操作温度范围, 如果长 期高温操作会加速催化剂晶粒增长, 表面积减少, 从而加速催化剂的衰老, 所 以必须使床层温度低于 280°C , 又由于床层温度低于 215 °C触媒可能有结蜡反 应, 因此, 最佳温度范围是 215 °C ~ 280°C。
通过计算, 由于配加转炉煤气后 CO和 C02浓度的增大, 将增加曱醇约 3.28t/h, 本实施例曱醇合成塔为管壳式合成塔, 根据测算增加 1吨曱醇将产生 约 0.93吨蒸汽, 于是, 本实施例中为了控制合成塔的温升, 在利用所述合成 气反应生成曱醇同时用水补充反应中失去的水分,即合成塔的壳层锅炉水副产 蒸汽来带走的水分,所述补充的锅炉水的量与曱醇产量按重量比优选为 0.90 ~ 0.96: 1 , 更优选为 0.93: 1 , 即补充水量约为 3.15t/h。
由合成气反应生成的曱醇为粗曱醇,因此,本实施例中还采用由预精馏塔、 加压塔和常压塔组成的三塔精馏技术对所述曱醇进行精馏, 制取得到精曱醇, 之后将精曱醇送至成品罐区贮存。
本发明实施例所公开的生产曱醇的方法,以炼钢生产中原本当作废气燃放 的副产气转炉煤气作为生产曱醇的原料, 其组成中 CO含量较高, 而 CO也是 一种宝贵的化工原料,作为废气燃放既污染环境又浪费资源。 因此根据焦炉煤 气中氢元素多而碳元素少,转炉煤气中碳元素多而氢元素少的情况,将两种气 体按一定比例混合后做为生产曱醇的原料,既解决了单纯采用焦炉煤气做原料 而导致的氢气消耗不完, 曱醇合成率低, 资源浪费的问题, 又减少了环境的污 染, 从经济角度, 利用废气做工业原料, 也降低了生产成本。
本发明还提供了一种生产曱醇的设备, 参见图 1 , 包括:
与转炉煤气排气口相连的转炉煤气净化装置 1 ;
与焦炉煤气排气口和所述转炉煤气净化装置 1 的排气口相连的混合装置 2, 本实施例中的混合装置 2为焦炉煤气管道, 在焦炉煤气管道处设一开口通 入净化后的转炉煤气, 焦炉煤气与净化后的转炉煤气混合, 得到混合气;
与混合装置 1 相连的混合气压缩机 3 , 混合气压缩机 3 将混合气加压 至 .2Mpa ~ 2.8Mpa;
与混合气压缩机 3的排气口相连的脱硫装置 4;
与脱 装置 4的排气口相连的转化装置 5 , 在转化装置 5中脱 后的混合 气被转化为包括一氧化碳和氢气的合成气, 所述合成气中氢碳比按体积比 ( H -C02) / (C0+C02) =2.0 - 2.05;
与转化装置 5的排气口相连的合成气压缩机 6, 合成气压缩机 6为合成气 力口压至 5.5Mpa ~ 6.5 Mpa;
与合成气压缩机 6的排气口相连的管壳式的合成塔 7, 在合成塔 7中利用 合成气反应生成曱醇;
与转化装置 5、 焦炉煤气排气口和所述转炉煤气净化装置排气口相连的控 制器,控制器通过实时监测合成气的氢碳比来调整净化后的转炉煤气与焦炉煤 气的流量, 以控制净化后的转炉煤气与焦炉煤气的混合比例, 所述混合比例为 按体积比净化后转炉煤气: 焦炉煤气 =0.8 ~ 1.2: 9.2 ~ 8.8。
其中, 本实施例中的脱硫装置 4、 转化装置 5、 合成气压缩机 6以及合成 塔 7统称为利用混合气反应生成曱醇的合成装置。
另外,还包括与合成塔 7相连,对合成塔 7产生的曱醇进行精馏的预精馏 塔 8、 加压塔 9和常压塔 10。
本领域技术人员可以理解,净化后的转炉煤气与焦炉煤气的混合可以在焦 炉煤气管道处也可以在混合气压缩机中, 或者设置其他的混合装置,但混合装 置的选择并不影响本发明的保护范围。
下面结合图 1 和方法实施例说明本实施例公开的生产曱醇的设备和工艺 流程:
来自炼钢过程的转炉煤气经过转炉煤气净化装置 1中的水除尘装置、鼓风 机、 气液分离器、 吸附净化单元以及精制单元后, 对转炉煤气进行降温, 并除 去其中的粉尘以及对合成和转化催化剂有害的硫、 磷、 砷、 氟等杂质, 得到满 足反应要求的净化的转炉煤气, 净化后的转炉煤气的标准为: P¾<lPPm; C0S<lPPm ; HF<0. lPPm; AsH3 <5PPb; H2S<lPPm, 来自转炉的转炉煤气经过处理 后达到上述标准后, 与来自焦炉的焦炉煤气混合得到混合气。
焦炉煤气在与净化后的转炉煤气混合前在焦化厂经过预处理。所述预处理 过程为:
焦炉煤气在鼓风机后设经电捕焦油器将焦炉煤气中的焦油脱至 50mg/Nm3 以下;
在鼓风机后的硫铵工段采用酸洗法将焦炉煤气中的氨脱至 50mg/Nm3以 下;
采用横管式间冷器, 循环喷洒冷凝液将焦炉煤气中的蔡脱至 100mg/Nm3 以下;
采用焦油洗油进行循环洗涤的方式, 将焦炉煤气中的苯类降至 2g/Nm3以 下;
采用 PDS法将焦炉煤气中的硫化氢、 氰化氢降至 20mg/Nm3以下。 比例混合并压缩至 2.2Mpa ~ 2.8Mpa后,进入脱直装置 4对混合气进行精脱硫,
将总硫脱至 O.lppm以下, 脱硫后的气体与来自外界的氧气混合, 采用纯氧催 化部分氧化工艺在转化装置 5中进行转化,将混合气体中的曱烷及少量多碳烃 转化为合成曱醇的有用成分一氧化碳、二氧化碳和氢气, 即生产曱醇所需的合 成气, 之后经合成气压缩机 6将合成气加压至 5.5Mpa ~ 6.5 Mpa, 加压后的合 成气在合成塔 7中反应生成粗曱醇,通过向合成塔中补充一定量的锅炉水将反 应温度需控制在 215 °C ~ 280°C范围内, 之后利用三塔精馏技术精馏粗曱醇得 到精曱醇。
其中, 净化后的转炉煤气与焦炉煤气的混合比例的控制方式为,通过实时 监测合成气中的氢碳比,根据氢碳比的变化, 实时的调整转炉煤气和焦炉煤气 的流量。 在生产过程中, 合成塔 7中未完全反应的气体有多处去路, 比如作为 循环气返回合成气压缩机 6重复压缩后再次反应,或者是返回转化装置 5作为 预热炉或升温炉的热源利用,也可以作为焦炉加热的热源利用, 或者将驰放气 中的氢提取出来做为氢源利用, 即将驰放气经变压吸附装置提取氢, 具体措施 为本领域技术人员所公知的, 这里不再赘述,但是对合成塔中未完全反应的气 体的处理方式并不能影响本发明实施例的保护范围。
需要说明的是, 在脱硫装置 4中进行的脱硫主反应如下:
RSH+H2= H2S+RH;
RSR+2H2= H2S+2RH;
COS+H2= H2S+CO;
CS2+2H20 = 2H2S+CO+C02;
H2S+FeO = FeS+H20;
H2S+ZnO = ZnS+H20。
其中, 克醇 RSH、 克醚 RSR、 RrS-R2和 CS2均为焦炉煤气中的杂质。 在转化装置 5中进行的纯氧催化部分氧化过程主反应如下:
2H2+02 = H20+115.48kcal;
2CH4+02 = 2CO+4H2+17.0kcal;
CH4+H20 = CO+3H2-49.3kcal;
CH4+C02= 2CO+2H2-59.1kcal;
CO+H20 = C02+H2+9.8kcal。
其中, 反应后生成的 co、 co2 和 ¾即为合成气的主要成分, 合成气中 的氢碳比需控制在 2.0 ~ 2.05。
CO+2H2= CH3OH+Q;
C02+3H2 = CH3OH+H20+Q。 进行描述。
实施例一
以钢焦联产企业产出的焦炉煤气和转炉煤气为原料,在某一时刻,原料的 组成为:
转炉煤气净化前后成分及杂质情况为:
在加入转炉煤气前, 焦炉煤气及转化后的合成气的组成情况为:
项 目 H2 CO co2 CH4 N2 CmHn 02 ∑ 焦炉气 56. 52 7. 54 2. 96 26. 91 2. 80 2. 75 0. 52 100 合成气 71. 42 11. 42 11. 86 0. 83 4. 13 0. 00 0. 34 100
在此刻,在线分析单独使用焦炉煤气转化为曱醇所需合成气后的有效成份 所占合成气比例为: ¾为 71.42%; CO为 11.42%; C02为 11.86%。 合成气在 进合成气压缩机前温度控制在 40 °C以下,压力在 2.0Mpa左右,此时合成气的 氢碳比 F= ( H-C02) I (C0+C02) = (71.42-11.86)/(11.42+11.86)=2.56, 由此可知: 此 时合成气中氢含量偏高, 需要补加碳, 所需补加的碳源为转炉煤气, 转炉煤气 净化后有用成份为: CO为 63.22%; C02为 13.30%; ¾为 3.50%, 净化后的 转炉煤气温度控制在 40 °C以下, 压力在 O.OlMpa以下。 假设某时刻合成气的 流量为 30000Nm3/h, 根据合理氢碳比要求, F取值 2.02, 设配加的转炉气量 为 XNmVh, 计算式为:
F==( H-C02) I (C0+C02) = {(30000*71.42+3.5*X )-( 30000*11.86+13.30*X )} I {30000* ( 11.42+11.86) + (63.22+13.30) *X} =2.02;
X=2288Nm7h;
即可算出此时所需转炉煤气的气量为 2288Nm3/h。
加转炉煤气前后合成气成分及氢碳比对照表为:
依照上述方法随时调节转炉煤气的最佳通入量,将混合气转化后生成的曱 醇合成气, 经合成气压缩机加压至 6.0Mpa, 再进入曱醇合成塔得到粗曱醇。 曱醇合成采用 6.0MPa低压合成技术, 合成塔采用管壳式, 合成所得的粗曱醇 采用预精馏塔、加压塔和常压塔三塔精馏技术制取精曱醇,产品精曱醇送至成 品罐区贮存, 经测试, 此工艺生产的曱醇产品质量达到 GB338-2004优等品的 水平。
加转炉煤气前后曱醇驰放气含量对比表为:
项 目 CO C02 02 CH4 N2 加转炉气前 v% 77.59 2.96 7.65 0.13 4.16 7.51 加转炉气后 v% 63.70 5.79 10.80 0.26 4.87 14.58
从以上数据可以看出, 转炉煤气加入后, 驰放气中 ¾的含量占驰放气总 量由 77.59%降^ 为 63.70%, 降^ 了 13.8%, 可见加入转炉煤气后 H2的利用率 提高了, 排放量减少了。 另外, 本实施例中由于提高了原料的利用率, 将废气 作为原料气, 提高了经济效益, 同时也降低了环境污染。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指 出, 对于本技术领域的普通技术人员来说, 在不脱离本发明原理的前提下, 还 可以对本发明进行若干改进和修饰,这些改进和修饰也落入本发明权利要求的 保护范围内。
对所公开的实施例的上述说明,使本领域专业技术人员能够实现或使用本 发明。 对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见 的, 本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下, 在 其它实施例中实现。 因此, 本发明将不会被限制于本文所示的这些实施例, 而 是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
+
Claims
1、 一种生产曱醇的方法, 其特征在于, 包括:
净化转炉煤气;
将净化后的转炉煤气与焦炉煤气混合, 得到混合气;
利用所述混合气反应生成曱醇。
2、 根据权利要求 1所述的方法, 其特征在于, 净化转炉煤气的过程包括: 对转炉煤气加压;
除去加压后的转炉煤气中的机械水;
吸附除去机^ ^水后的转炉煤气中的杂质;
对吸附杂质后的转炉煤气进行脱砷, 得到净化后的转炉煤气。
3、 根据权利要求 1所述的方法, 其特征在于, 利用所述混合气反应生成 曱醇的过程包括:
对所述混合气进行脱
采用纯氧催化部分氧化转化工艺转化脱硫后的混合气, 得到合成气; 利用所述合成气在 215 °C ~ 280°C , 5.5Mpa ~ 6.5 Mpa条件下反应生成曱 醇。
4、 根据权利要求 3所述的方法, 其特征在于, 净化后的转炉煤气与焦炉 煤气的混合过程为,根据所述合成气中的氢碳比调整净化后的转炉煤气与焦炉 煤气的混合比例后进行混合, 所述合成气中氢碳比按体积比 ( H -C02) I (C0+C02) =2·0 ~ 2·05。
5、 根据权利要求 3所述的方法, 其特征在于, 对所述混合气进行脱硫前 还包括: 将所述混合气加压至 2.2Mpa ~ 2.8Mpa。
6、根据权利要求 3所述的方法, 其特征在于, 利用所述合成气在 215 °C ~ 280 °C , 5.5Mpa ~ 6.5 Mpa条件下反应生成曱醇。
7、 根据权利要求 6所述的方法, 其特征在于, 利用所述合成气反应生成 曱醇同时用水补充反应中失去的水分,所述补充的水的量与曱醇产量按重量比 0.90 - 0.96: 1。
8、 根据权利要求 1-7任一项所述的方法, 其特征在于, 还包括对所述曱 醇进行精馏, 得到精曱醇。
9、 一种生产曱醇的设备, 其特征在于, 包括:
与转炉煤气排气口相连的转炉煤气净化装置;与焦炉煤气管道和所述转炉 煤气净化装置排气口相连的混合装置;
与所述混合装置排气口相连的合成装置;
与所述合成装置、焦炉煤气管道和所述转炉煤气净化装置排气口相连的控 制器。
10、 根据权利要求 9所述的设备, 其特征在于, 所述合成装置包括: 与所述混合装置排气口相连的脱硫装置;
与所述脱硫装置排气口相连的转化装置;
与所述转化装置排气口相连的合成塔。
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---|---|---|---|---|
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Families Citing this family (3)
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DE102013113933A1 (de) * | 2013-12-12 | 2015-06-18 | Thyssenkrupp Ag | Verfahren zur Erzeugung von Synthesegas im Verbund mit einem Hüttenwerk |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1373113A (zh) * | 2002-03-20 | 2002-10-09 | 郭拥军 | 一种焦炉气合成甲醇的方法 |
CN102079689A (zh) * | 2009-11-30 | 2011-06-01 | 四川达兴能源股份有限公司 | 生产甲醇的方法和设备 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3515250A1 (de) * | 1985-04-27 | 1986-10-30 | Hoesch Ag, 4600 Dortmund | Verfahren zur herstellung von chemierohstoffen aus koksofengas und huettengasen |
EA008569B1 (ru) * | 2003-11-19 | 2007-06-29 | Эксонмобил Кемикэл Пейтентс Инк. | Регулирование отношения этилена к пропилену, получаемых в процессе превращения кислородсодержащего вещества в олефины |
-
2011
- 2011-04-28 WO PCT/CN2011/073445 patent/WO2012145910A1/zh active Application Filing
- 2011-04-28 EP EP11864561.3A patent/EP2657215B1/en not_active Not-in-force
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1373113A (zh) * | 2002-03-20 | 2002-10-09 | 郭拥军 | 一种焦炉气合成甲醇的方法 |
CN102079689A (zh) * | 2009-11-30 | 2011-06-01 | 四川达兴能源股份有限公司 | 生产甲醇的方法和设备 |
Non-Patent Citations (2)
Title |
---|
LI KEBING ET AL.: "New Technique of Comprehensive Utilization of Coke Oven Gas and Converter Coal Gas.", CHEMICAL INDUSTRY AND ENGINEERING PROGRESS. 1000-6613, vol. 29, no. S1, 2010, pages 325 - 327, XP008169502 * |
See also references of EP2657215A4 * |
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US10697031B2 (en) | 2013-12-12 | 2020-06-30 | Thyssenkrupp Ag | Combined system for producing steel and method for operating the combined system |
US10781498B2 (en) | 2013-12-12 | 2020-09-22 | Thyssenkrupp Ag | Combined system for producing steel and method for operating the combined system |
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