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    • 1. 发明授权
    • Production of methanol
    • 生产甲醇
    • US4271086A
    • 1981-06-02
    • US35964
    • 1979-05-04
    • Emil SuppHeinz JockelGerhard CorneliusFriedmann Marschner
    • Emil SuppHeinz JockelGerhard CorneliusFriedmann Marschner
    • C07C29/15B01J23/00C01B3/38C07B61/00C07C27/00C07C29/151C07C29/154C07C31/04C07C67/00C07C27/06
    • C07C29/1518C01B3/38Y02P20/52
    • In the production of methanol from gaseous hydrocarbons having a lower C/H ratio than is stoichiometrically required to produce methanol and comprising the steps of catalytically cracking said hydrocarbons in the presence of water vapor at about 830.degree. to 930.degree. C. and about 5 to 30 bars to produce a synthesis gas consisting essentially of hydrogen and oxides of carbon, and subsequently catalytically converting said synthesis gas of hydrogen and oxides of carbon to methanol at about 230.degree. to 280.degree. C. and about 30 to 150 bars, the improvement which comprises transferring heat from the hot synthesis gas to the hydrocarbon-water vapor mixture flowing through the cracking catalyst thereby providing at least part of the heat required for the catalytic cracking of the hydrocarbons and reducing the consumption of thermal-/energy per unit of methanol produced. Advantageously, heat transfer is effected by passing the hot synthesis gas through a convoluted or corrugated tube embedded in the hydrocarbon cracking catalyst. Gaseous carbon-containing constituents of the methanol synthesis exhaust gas are removed by adsorption, and desorption; CO.sub.2 may later be removed from the residual methanol synthesis exhaust gas by methanol scrubbing and subsequent stripping, both the desorbed constituents and the CO.sub.2 being mixed with the hydrocarbons before they are cracked, whereby the C/H ratio of the hydrocarbon feed is raised and the consumption of the thermal-/energy per unit of methanol produced is reduced.
    • 在生产甲醇的过程中,C / H比C / H比低于生产甲醇所需要的化学计量比的气态烃,并且包括在水蒸气存在下在约830-930℃和约5℃下催化裂化所述烃的步骤 30巴以产生基本上由氢和碳的氧化物组成的合成气,随后将氢的合成气和碳的氧化物在约230℃至280℃和约30至150巴下催化转化成甲醇,其改进是 包括将热量从热合成气转移到流过裂解催化剂的烃 - 水蒸汽混合物,从而提供烃的催化裂化所需的至少一部分热量,并减少每单位产生的甲醇的热能/能量消耗 。 有利地,通过使热合成气通过嵌入在烃裂化催化剂中的卷积或波纹管来实现热传递。 通过吸附除去甲醇合成废气的气态含碳成分,解吸; 随后可以通过甲醇洗涤和随后的汽提将二氧化碳从残留的甲醇合成废气中除去,解吸组分和二氧化碳在烃裂解前与烃混合,从而提高烃进料的C / H比 消耗每单位产生的甲醇的热能/能量减少。
    • 2. 发明授权
    • Process of producing methanol
    • 生产甲醇的方法
    • US4203915A
    • 1980-05-20
    • US945727
    • 1978-09-25
    • Emil SuppHeinz JockelHagen KrummFriedemann Marschner
    • Emil SuppHeinz JockelHagen KrummFriedemann Marschner
    • B01B1/00C01B3/38C07C29/151C07C31/04C07C31/06
    • C07C29/1518B01B1/005C01B3/38C07C29/1512
    • In the production of methanol from gaseous and liquid hydrocarbons having a higher C/H ratio than is stoichiometrically required to produce methanol, wherein said hydrocarbons are catalytically cracked in the presence of water vapor and at a temperature of about 350.degree.-950.degree. C. and under a pressure of about 5-30 bars to produce a synthesis gas containing hydrogen and oxides of carbon, followed by a catalytic reaction of the hydrogen with the oxides of carbon at a temperature of about 230.degree.-280.degree. C. and under a pressure of about 30-150 bars to produce methanol, the improvement which comprises treating the methanol synthesis exhaust gas so as to remove therefrom carbonaceous gaseous constituents so that the residual gas is high in hydrogen, and adding said high-hydrogen residual gas to the hydrocarbons prior to cracking in an amount such that the C/H ratio of the material to be cracked is up to about 5.7, thereby reducing the energy consumption per unit of methanol produced. Advantageously, the cracking of said hydrocarbons is effected in two stages, the carbonaceous gaseous constituents removed from the methanol synthesis exhaust gas being used for indirect heating of the second cracking stage. The removal of the carbonaceous gaseous constituents from the methanol synthesis exhaust gas is effected by contacting such exhaust gas with a molecular sieve, at least part of the high-hydrogen residual gas being added to the hydrocarbons before the second stage, the mixture of hydrocarbons and high-hydrogen residual gas being treated to effect hydrogenation and desulfurization of the hydrocarbons.
    • 在生产甲醇时,由具有比化学计量学上要求的甲醇高的C / H比的气态和液态烃生产甲醇,其中所述烃在水蒸汽存在下和约350-950℃的温度下被催化裂解。 并且在约5-30巴的压力下产生含有氢和碳氧化物的合成气,然后在约230℃-280℃的温度下将氢与碳氧化物进行催化反应,并在 约30-150巴的压力产生甲醇,其改进包括处理甲醇合成废气以从其中除去含碳气体成分,使得残余气体的氢气高,并将高氢残留气体加入烃中 在使裂化材料的C / H比高达约5.7的量开裂之前,从而降低每单位产生的甲醇的能量消耗。 有利地,所述烃的裂化分两个阶段进行,从甲醇合成废气中除去的含碳气体成分用于第二裂解阶段的间接加热。 从甲醇合成废气中除去含碳气体成分是通过使这种废气与分子筛接触,至少部分高氢残余气体在第二阶段之前加入到烃中,烃的混合物和 处理高氢残余气体以进行烃的氢化和脱硫。
    • 5. 发明授权
    • Process of producing methanol
    • 生产甲醇的方法
    • US5364887A
    • 1994-11-15
    • US143807
    • 1993-10-27
    • Peter KonigFriedrich-Wilhelm MollerEmil Supp
    • Peter KonigFriedrich-Wilhelm MollerEmil Supp
    • C07C29/151C07C27/06
    • C07C29/1516Y02P20/52
    • Methanol is catalytically produced from a synthesis gas which contains H.sub.2, CO and CO.sub.2 in a synthesis reactor at temperatures from 220.degree. to 300.degree. C. and under a pressure in the range from 20 to 120 bars. A product mixture which contains methyl formate is withdrawn from the synthesis reactor and is cooled to temperatures in the range from 20.degree. to 60.degree. to provide a condensate which contains methanol, water and methylformate. A gas mixture which contains H.sub.2, CO and CO.sub.2 is formed at the same time. A fraction which comprises 10 to 100% by weight methyl formate is separated from the condensate and is admixed with the synthesis gas which is fed to the synthesis reactor.
    • 在合成反应器中,在220〜300℃的温度下,在20〜120巴的压力下,由含有H 2,CO,CO 2的合成气催化生成甲醇。 含有甲酸甲酯的产物混合物从合成反应器中取出并冷却至20℃至60℃的温度,以提供含有甲醇,水和甲酸甲酯的冷凝物。 同时形成含有H 2,CO和CO 2的气体混合物。 将含有10至100重量%甲酸甲酯的馏分与冷凝物分离,并与供入合成反应器的合成气混合。
    • 9. 发明授权
    • Method of obtaining improved equilibrium conditions and of
simultaneously producing steam under high pressure in the production of
methanol
    • 在甲醇生产中获得改进的平衡条件并同时生产高压蒸汽的方法
    • US4369255A
    • 1983-01-18
    • US287007
    • 1981-07-27
    • Emil Supp
    • Emil Supp
    • C07C29/15B01J8/00B01J8/06B01J23/72C07B61/00C07C27/00C07C29/151C07C29/152C07C29/154C07C31/04C07C67/00C07C27/06
    • B01J8/067B01J8/0005C07C29/1512C07C29/152B01J2208/0007B01J2208/00212B01J2208/00256Y02P20/52
    • A method of controlling the equilibrium conditions and of simultaneously producing steam under high pressure in the production of methanol by a reaction of oxides of carbon and of hydrogen-containing gases at temperatures of 200.degree. to 300.degree. C. under a pressure of 20 to 100 bars at a copper-containing catalyst, which is contained within the reactor in tubes, which are indirectly cooled by boiling water under pressure, wherein the resulting steam is withdrawn together with circulating water and is separated from the water, the water is recycled and the evaporated water is replaced by feed water. According to the invention the process is carried out in such a manner that a perforated thin intermediate bottom plate is provided in the reactor spaced 20 to 150 cm over the lower tube plate, the reactor is fed with the circulating water above that intermediate bottom and with feed water below that intermediate bottom, the gaseous reaction mixture is cooled by 20.degree. to 50.degree. C. in the lower part of the catalyst-filled tubes in a tube length of 20 to 150 cm, the feed water is heated in the reactor to temperatures of 230.degree. to 290.degree. C. with evaporation of part of the feed water, the resulting mixture of steam and circulating water is separated, the circulating water is recycled and the resulting high-pressure steam is withdrawn. In this method, steam under a pressure above 60 bars can be produced whereas only a pressure of 40 bars has been reached heretofore.
    • 在200〜300℃的温度下,在20〜100℃的压力下,通过碳和含氢气体的氧化物的反应,在高压生产中同时制造高压蒸汽的方法 包含在管内的反应器内的含铜催化剂的棒,其在压力下由沸水间接冷却,其中所得蒸汽与循环水一起取出并与水分离,水被再循环, 蒸发水由给水代替。 根据本发明,该方法是这样一种方式进行的:在反应器上设置穿孔薄的中间底板,反应器在下管板上隔开20至150厘米,反应器内供给循环水, 在低于该中间底部的水中加入水,将气体反应混合物在20至150cm的管长度的催化剂填充管的下部中冷却20至50℃,将反应器中的给水加热至 温度为230°至290°C,蒸发部分进料水,蒸汽和循环水混合物分离,循环水再循环,得到高压蒸汽。 在该方法中,可以产生在60巴以上的压力下的蒸汽,而迄今为止仅达到了40巴的压力。