公开(公告)号：US5310506A

公开(公告)日：1994-05-10

申请号：US120140

申请日：1993-09-10

Applicant: Emil Supp ,  Rainer Morgenroth

Inventor： Emil Supp ,  Rainer Morgenroth

IPC: C01B3/38 ,  C07C29/151 ,  C01B3/36

CPC classification number: C01B3/38 ,  C07C29/1518 ,  C01B2203/0244 ,  C01B2203/043 ,  C01B2203/061 ,  C01B2203/0844 ,  C01B2203/0883 ,  C01B2203/1011 ,  C01B2203/1058 ,  C01B2203/1241 ,  C01B2203/142 ,  C01B2203/148 ,  C01B2203/82

Abstract: In a reforming reactor operated with reactor outlet temperatures from 600.degree. to 1300.degree. C. and under a pressure from 10 to 100 bars, a methane-containing hydrocarbon gas is reacted with oxygen and water vapor. The reforming reactor is additionally fed with a high-hydrogen gas, which contains free hydrogen. The raw synthesis gas withdrawn from the reforming reactor is mainly composed of hydrogen, carbon monoxide and carbon dioxide. Without a removal of carbon dioxide from the raw synthesis gas, a synthesis gas is produced, which is suitable for the methanol synthesis and in which the concentrations of the components H.sub.2, CO and CO.sub.2 have a molar ratio (H.sub.2 -CO.sub.2): (CO+CO.sub.2), called the stoichiometric number, from 1.97 to 2.2. In case of need, the stoichiometry number can be adjusted by adding hydrogen to the raw synthesis gas coming from the reforming reactor.

Abstract translation: 在反应器出口温度为600〜1300℃，压力为10〜100巴的重整反应器中，含甲烷的烃类气体与氧气和水蒸汽反应。 重整反应器另外加入含有游离氢的高氢气。 从重整反应器排出的原始合成气主要由氢，一氧化碳和二氧化碳组成。 没有从原料合成气中除去二氧化碳，产生适合于甲醇合成的合成气，其中组分H 2，CO和CO 2的浓度具有摩尔比（H 2 -CO 2）：（CO + CO2），称为化学计量数，从1.97到2.2。 在需要的情况下，可以通过向来自重整反应器的原料合成气中加入氢来调节化学计量数。

公开(公告)号：US5364887A

公开(公告)日：1994-11-15

申请号：US143807

申请日：1993-10-27

Applicant: Peter Konig ,  Friedrich-Wilhelm Moller ,  Emil Supp

Inventor： Peter Konig ,  Friedrich-Wilhelm Moller ,  Emil Supp

IPC: C07C29/151 ,  C07C27/06

CPC classification number: C07C29/1516 ,  Y02P20/52

Abstract: 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 A product mixture which contains methyl formate is withdrawn from the synthesis reactor and is cooled to temperatures in the range from 20.degree.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.

Abstract translation: 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。

公开(公告)号：US4271086A

公开(公告)日：1981-06-02

申请号：US35964

申请日：1979-05-04

Applicant: Emil Supp ,  Heinz Jockel ,  Gerhard Cornelius ,  Friedmann Marschner

Inventor： Emil Supp ,  Heinz Jockel ,  Gerhard Cornelius ,  Friedmann Marschner

IPC: C07C29/15 ,  B01J23/00 ,  C01B3/38 ,  C07B61/00 ,  C07C27/00 ,  C07C29/151 ,  C07C29/154 ,  C07C31/04 ,  C07C67/00 ,  C07C27/06

CPC classification number: C07C29/1518 ,  C01B3/38 ,  Y02P20/52

Abstract: 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.

Abstract translation: 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。

公开(公告)号：US4087449A

公开(公告)日：1978-05-02

申请号：US776078

申请日：1977-03-09

Applicant: Friedemann Marschner ,  Emil Supp ,  Gunter Pockrandt

Inventor： Friedemann Marschner ,  Emil Supp ,  Gunter Pockrandt

IPC: C07C29/151 ,  C07C29/154 ,  C07C29/16

CPC classification number: C07C29/1518 ,  C07C29/154 ,  C12C11/02

Abstract: A process for producing methanol wherein coal is gasified by a treatment with water vapor and oxygen at elevated temperature, the resulting gas is cooled and is scrubbed with an organic solvent to remove impurities from the gas, the carbon oxides contained in the gas are catalytically reacted with hydrogen to form methanol, and the methanol is separated, the improvement comprises subjecting the residual gas left after the separation of the methanol to a catalytic cracking treatment with water vapor under pressure and at elevated temperature to form hydrogen and carbon oxides and cooling the cracked gas and recycling it to the methanol synthesis.

Abstract translation: 一种生产甲醇的方法，其中通过在高温下用水蒸汽和氧气处理将煤气化，所得气体被冷却并用有机溶剂洗涤以从气体中除去杂质，气体中所含的碳氧化物被催化反应 用氢气形成甲醇，甲醇分离，改进包括在压力和升高的温度下，用水蒸汽分离甲醇后残留的残余气体进行催化裂化处理，形成氢和碳氧化物并冷却裂化 气体并将其回收到甲醇合成。

公开(公告)号：US4203915A

公开(公告)日：1980-05-20

申请号：US945727

申请日：1978-09-25

Applicant: Emil Supp ,  Heinz Jockel ,  Hagen Krumm ,  Friedemann Marschner

Inventor： Emil Supp ,  Heinz Jockel ,  Hagen Krumm ,  Friedemann Marschner

IPC: B01B1/00 ,  C01B3/38 ,  C07C29/151 ,  C07C31/04 ,  C07C31/06

CPC classification number: C07C29/1518 ,  B01B1/005 ,  C01B3/38 ,  C07C29/1512

Abstract: 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.

Abstract translation: 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。

公开(公告)号：US3962300A

公开(公告)日：1976-06-08

申请号：US568532

申请日：1975-04-15

Applicant: Heinz Hiller ,  Gerhard Hochgesand ,  Emil Supp ,  Friedemann Marschner ,  Gerhard Grunewald

Inventor： Heinz Hiller ,  Gerhard Hochgesand ,  Emil Supp ,  Friedemann Marschner ,  Gerhard Grunewald

IPC: C01B3/12 ,  C01B3/22 ,  C01B3/36 ,  C01B3/50 ,  C07C29/151 ,  F25J3/02 ,  F25J3/04 ,  C07C29/16

CPC classification number: C01B3/12 ,  C01B3/22 ,  C01B3/36 ,  C01B3/50 ,  C07C29/1518 ,  F25J3/0223 ,  F25J3/0285 ,  F25J3/04018 ,  F25J3/04036 ,  F25J3/04121 ,  F25J3/04545 ,  C01B2203/0475 ,  C01B2203/0485

Abstract: Methanol is produced by a process wherein1. sulfur-containing high-boiling hydrocarbons are subjected to a partial oxidizing treatment with oxygen and water vapor at a pressure which is at least 5 kilograms and preferably 10-15 kilograms per square centimeter above the pressure of the methanol synthesis to produce a raw gas;2. the raw gas is desulfurized and is subsequently treated with water vapor to convert part of its carbon monoxide content into hydrogen and carbon dioxide;3. thereafter the converted gas from step (2) is scrubbed to remove at least part of the carbon dioxide;4. methanol is produced by a reaction of the resulting synthesis gas from step (3) in contact with a copper-containing catalyst, which is indirectly cooled with water boiling under superatmospheric pressure resulting in the production of high-pressure steam; and5. the high-pressure steam produced by the exothermic heat of formation of the methanol in step (4) is expanded by generating power to produce compression energy for the gases to be compressed in the process.

Abstract translation: 甲醇是通过以下方法生产的：其中1.含硫的高沸点碳氢化合物被氧化和水蒸气处理至少有5个KILOGRAMS和优选的10-15千克每平方厘米的压力下的氧气处理。 甲醇合成生产原料气体; 2.原料经脱硫处理，并经过水蒸气处理，将其一氧化碳含量的一部分转化为氢气和二氧化碳; 3.从步骤（2）转换出的气体被清除，以移除二氧化碳的至少一部分; 甲醇是由与步骤（3）的结果合成气体反应产生的，与含铜催化剂接触，该催化剂在生产高压蒸汽的情况下，根据超级压力结合水热锅炉间歇性冷却; 和（5）在步骤（4）中由甲烷的形成热产生的高压蒸汽通过产生用于在该方法中压缩的气体产生压缩能量的能力而扩展。

公开(公告)号：US4369255A

公开(公告)日：1983-01-18

申请号：US287007

申请日：1981-07-27

Applicant: Emil Supp

Inventor： Emil Supp

IPC: C07C29/15 ,  B01J8/00 ,  B01J8/06 ,  B01J23/72 ,  C07B61/00 ,  C07C27/00 ,  C07C29/151 ,  C07C29/152 ,  C07C29/154 ,  C07C31/04 ,  C07C67/00 ,  C07C27/06

CPC classification number: B01J8/067 ,  B01J8/0005 ,  C07C29/1512 ,  C07C29/152 ,  B01J2208/0007 ,  B01J2208/00212 ,  B01J2208/00256 ,  Y02P20/52

Abstract: 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.

Abstract translation: 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。

公开(公告)号：US4045960A

公开(公告)日：1977-09-06

申请号：US647965

申请日：1976-01-09

Applicant: Gerhard Cornelius ,  Friedemann Marschner ,  Emil Supp ,  Toma Varlam

Inventor： Gerhard Cornelius ,  Friedemann Marschner ,  Emil Supp ,  Toma Varlam

IPC: F02C6/10 ,  F01K17/00

CPC classification number: F02C6/10

Abstract: The sensible heat contained in exhaust gases formed in chemical reactions is utilized to produce energy. The exhaust gas is conducted as a counterflow to the product gas and is heated and expanded with the performance work.

Abstract translation: 在化学反应中形成的排气中所含的显热用于产生能量。 废气作为与产品气体的逆流进行传导，并通过性能工作被加热和膨胀。

公开(公告)号：US4854943A

公开(公告)日：1989-08-08

申请号：US292700

申请日：1989-01-03

Applicant: Theodor Voeste ,  Emil Supp

Inventor： Theodor Voeste ,  Emil Supp

IPC: C01B32/50 ,  B01J8/02 ,  B01J8/04 ,  C01B3/38 ,  C10G11/00 ,  C10J3/46 ,  C10K3/00 ,  C10K3/02

CPC classification number: C01B3/384 ,  B01J8/0257 ,  B01J8/048 ,  C10K3/02 ,  C01B2203/0811

Abstract: Gases which are rich in carbon monoxide are producted by a catalytic cracking of gaseous or vaporized hydrocarbons. A part of the hydrocarbons is combusted with an oxygen-containing gas which is added at a rate that is twice to ten times the stoichiometric oxygen demand. The combustion temperature are between 800.degree. and 1500.degree. C. The oxygen-containing combustion gas is admixed to the preheated remainder of the hydrocarbon and a mixture is producted which is at a temperature between about 700.degree. and about 1300.degree. C. That mixture is passed through a fixed bed consisting of a granular cracking catalyst. A high-CO product gas at a temperature between about 800.degree. and about 1150.degree. C. is withdrawn from the fixed bed.

Abstract translation: 富含一氧化碳的气体是通过气态或气化烃的催化裂化产生的。 一部分烃类与含氧气体一起燃烧，其含量是化学计量氧气需求量的两倍至十倍。 燃烧温度在800〜1500℃之间。含氧燃烧气体与预热的碳氢化合物的其余部分混合，产生温度在约700℃至约1300℃之间的混合物。该混合物为 通过由粒状裂化催化剂组成的固定床。 约800至约1150℃之间的高CO产物气体从固定床中排出。

公开(公告)号：US4559207A

公开(公告)日：1985-12-17

申请号：US555860

申请日：1983-11-28

Applicant: Heinz Hiller ,  Emil Supp ,  Friedemann Marschner ,  Hans Kupfer ,  Lutz Weidemann

Inventor： Heinz Hiller ,  Emil Supp ,  Friedemann Marschner ,  Hans Kupfer ,  Lutz Weidemann

IPC: C07C29/15 ,  B01J8/06 ,  C07C27/00 ,  C07C29/152 ,  C07C29/154 ,  C07C31/04 ,  C07C67/00 ,  C22C38/18 ,  B01J19/02

CPC classification number: C22C38/18 ,  B01J8/06 ,  C07C29/152 ,  C07C29/154 ,  B01J2208/00212

Abstract: A reactor is provided for producing methanol by the reaction of synthesis gases containing carbon oxides and hydrogen in contact with a copper containing catalyst positioned in the reactor in catalyst tubes surrounded by boiling water under pressure. The catalyst tubes are made from a metallic material which is catalytically inactive with respect to the methanol synthesis gas and have approximately the same coefficient of thermal expansion as the shell of the reactor. The catalyst tubes are made of a steel composed of mixed austeniticferritic structure and containing 10-30% by weight chromium.

Abstract translation: 提供反应器，用于通过使含有碳氧化物和氢气的合成气与位于反应器中的含铜催化剂接触的反应器反应生成甲醇，催化剂管由沸水在压力下包围。 催化剂管由相对于甲醇合成气催化失活的金属材料制成，并且具有与反应器的壳大致相同的热膨胀系数。 催化剂管由含有10-30重量％铬的混合奥氏体铁素体结构的钢制成。