PL10388B3

PL10388B3 - A method of producing valuable liquid products from various types of coal, tar, mineral oils and similar materials.

Info

Publication number: PL10388B3
Application number: PL10388A
Authority: PL
Filing date: 1927-11-23
Publication date: 1929-05-31

Description

Najdluzszy czas trwania patentu do 8 pazdziernika 1941 r.W patencie glównym Nr 6025 wskaza¬ no, iz przy otrzymywaniu cennych produk¬ tów plynnych z róznych gatunków wegla, smól, olejów mineralnych i materjalow po¬ dobnych zapomoca gazów redukujacych pod cisnieniem, a zwlaszcza wysokiem i w temperaturach wysokich, nalezy przestrze¬ gac warunku, aby czesci aparatury, styka¬ jace sie z gazami redulkujacemi, nie zawie¬ raly wolnego zelaza, niklu i kobaltu.Obecnie wykryto, iz stosujac rózne ga¬ tunki wegla, smól, olejów mineralnych, ich produktów destylacji, ekstracji i prze¬ ksztalcenia, pozostalosci i ciala podobne pod cisnieniem powyzej 50 atm w przy¬ padku nieobecnosci w gazach redukuja¬ cych wiekszych ilosci tlenku wegla, lub wiekszych ilosci cial prowadzacych do wy¬ twarzania sie w komorze reakcyjnej tlen¬ ku wegla, wystarczy wylaczyc z czesci a- paratury, stykajacych sie z cialem reagu- jacem, szkodliwe zelazo, nikiel, a miedz, tylko w przypadku obecnosci siarki. Pod szkodliwem zelazem i niklem nalezy rozu¬ miec metale w takiej postaci, ze sa one fi¬ zykalnie lub chemicznie nieodporne, lubtez z podlegajacemi obróbce materjalami wywoluja reakcje szkodliwe, wytwarzajac np. metan, koks, wywolujac polimeryzacje i t. d. Reakcje te wywoluje np, zelazo po¬ rowate, o wielkiej powierzchni, stopy ze¬ lazne o zbyt wielkiej zawartosci wegla.Podobnie jak zelazo i nikiel zachowuje sie równiez i miedz, w razie zawartosci siarki w obrabianym materjale. Natenczas wsku¬ tek oddzialywania siarki wytwarzaja sie gabczaste masy, zawierajace siarczek mie¬ dzi, i dzialajace nadzwyczaj szkodliwie, szczególnie, gdy wobec wadliwego ruchu wzglednego miedzy temi masami i obrabia- nemi materjalami osiadaja pomiedzy nie¬ mi ciagliwe produkty polimeryzacji oraz koks, W przypadku nieobecnosci siarki, mozna jednak zamiast powyzszych mate¬ rjalów stosowac miedz jak równiez i sre¬ bro lub ich stopy, albo materjaly zachowu¬ jace sie podobnie.Czesci aparatury, które nalezy ochra¬ niac mozna wykonac z glinu lub stopów wen obfitujacych, chromu, molibdenu, wol¬ framu, wanadu lub stopów zawierajacych chrom, najkorzystniej w ilosci ponad 10%, kobalt, molibden, wolfram, wanad, man¬ gan oddzielnie lub w polaczeniu, ewentual¬ nie zawierajacych znaczne ilosci niklu i nieznaczna ilosc wegla lub zawierajacych wegliki metali trudnotopliwych, szczególnie metali nalezacych do grup 5 i 6 ukladu perjodycznego, jako to weglik wolframo¬ wy albo tez powlec je wskazanemi tu sub¬ stancjami, W przypadku zaopatrzenia pod¬ legajacych ochronie czesci aparatury w po¬ wloke, nalezy przestrzegac, aby powloka ta miala grubosc i takie wlasnosci, izby po¬ zostawala trwala, W pewnych warunkach bywa rzecza korzystna sporzadzic z materjalów wyzei wspomnianych albo powlec niemi i inne czesci aparatury, a zwlaszcza czesci styka¬ jace sie w temperaturze powyzej 300° z materjalami zawierajacemi siarke lub we¬ glowodory. Jako takie czesci; aparatury wchodza tu w gre, np, przewody, doprowa¬ dzajace materjaly wyjsciowe, skoro wpro- * wadza sie je do komory reakcyjnej w sta¬ nie podgrzanym, lub przewody, odprowa¬ dzajace produkty reakcji i t, d. Scislych granic temperatury dla tych srodków zapo¬ biegawczych nie mozna podac, albowiem wahaja sie one i zaleza od wlasnosci che¬ micznych materjalu wyjsciowego, od ewen¬ tualnie uzytych katalizatorów i t, d.Wskazane malerjaly posiadaja odpor¬ nosc zwlaszcza przeciwko oddzialywaniu zwiazków siarkowych w obecnosci wodo¬ ru we wchodzacych w gre temperaturach powyzej 300 —• 350° i pod cisnienieniami np, od 50 do 200 i wiecej atmosfer, Mate¬ rjaly te zapobiegaja ponadto wydzielaniu wegla wskutek rozkladu weglowodorów i powstawaniu metanu.Z materjalów wzmiankowanych na szczególna uwage zasluguja stopy ubogie w wegiel, a zwlaszcza zawierajace drobne ilosci wegla, np, mniej niz 0,25%, jak np, stal, zawierajaca 24,2% Fe, 61,1% Ni, 11,93% Cr, 0,13% C, lub stal Kruppa V2A, albo WT2. Skoro uzyty stop jest dzieki pewnym skladnikom, np, zawarto¬ sci chromu, zbyt kruchy, natenczas moze sie okazac pozadana pewna zawartosc ni¬ klu. Podobnie jak zelazo, które mozna u- nieszkodliwic, dodajac don innych cial, mozna takze calkowicie wyrównac szkodli¬ we dzialanie niklu, tudziez innych sklad¬ ników, np. wegla, zapomoca domieszek in¬ nych. Mozna równiez stosowac z powodze¬ niem stopy otrzymywane w prózni, np. chromonikiel B. Heraus'a zawierajacy 24,2% Fe, 60,1% Ni, 133,8% Cr, 0,02% C.Mozna równiez stosowac weglik wolfra¬ mowy. Stosowane metale, stopy lub tym podobne produkty podobne lepiej jest uwol¬ nic, o ile mozna od zanieczyszczen, na gra¬ nicy ziarn, jak np. od tlenu, siarki, wegla i t. d. Mozna to osiagnac np. w ten sposób, ze metale lub stopy o wlasnosciach zwy¬ klych traktuje sie w wysokich telnperatu- — 2 —rach gazami, np, wilgotnymi wodorem, które reaguja z zanieczyszczeniami, wytwarza¬ jac zwiazki lotne, W ten sposób osiaga sie mocna strukture krystaliczna, która, szcze¬ gólnie przy powierzchni gladkiej nawet przy silnych naprezeniach pokrytych nia lub wykonanych z niej czesci aparatu¬ ry, nie poddaje sie oddzialywaniu. PLThe longest term of the patent until October 8, 1941 In the main patent No. 6025 it was indicated that in obtaining valuable liquid products from various types of coal, tar, mineral oils and similar materials, reducing gases under pressure, especially high and at temperatures high, it must be ensured that the parts of the apparatus that come into contact with the reductant gases do not contain free iron, nickel and cobalt. It has now been found that using various types of coal, tar, mineral oils, their distillation products , extraction and transformation, residues and the like under a pressure of more than 50 atm in the case of the absence in reducing gases of greater amounts of carbon monoxide, or greater amounts of bodies leading to the production of carbon monoxide in the reaction chamber, it is sufficient Exclude harmful iron, nickel and copper from the parts of the apparatus that are in contact with the body, only in the presence of sulfur. Under harmful iron and nickel, it is necessary to understand metals in such a form that they are physically or chemically unresistant, or that they develop harmful reactions with the processed materials, producing, for example, methane, coke, causing polymerization, etc. These reactions are caused, for example, by iron rough, large surface, ferrous alloys with too much carbon content. Like iron and nickel, copper also behaves if there is sulfur in the material. Then, the interaction of sulfur produces spongy masses, containing copper sulphide, and extremely harmful, especially when, due to the defective relative movement between these masses and the materials being processed, tough polymerization products and coke settle between them. In the absence of sulfur, however, copper may be used instead of the above materials, as well as silver or their alloys, or materials behaving similarly. The parts of the apparatus to be protected may be made of aluminum or alloys of abundant baths, chromium, molybdenum , tungsten, vanadium or chromium-containing alloys, most preferably in an amount greater than 10%, cobalt, molybdenum, tungsten, vanadium, manganese, alone or in combination, possibly containing significant amounts of nickel and a small amount of carbon or carbon-containing refractory metals , especially metals belonging to groups 5 and 6 of the periodic system, as they are tungsten carbide or coat them with the indicated here If the parts of the apparatus to be protected are supplied with a half-shell, it must be ensured that the coating has a thickness and such properties that the chamber remains durable. Under certain conditions, it may be advantageous to make up the above-mentioned materials or to coat them with and other parts of the apparatus, in particular parts which come into contact at a temperature above 300 ° with materials containing sulfur or hydrocarbons. As such parts; apparatus are included here, for example, the conduits supplying the starting materials, since they are introduced into the reaction chamber in a heated state, or the conduits discharging the reaction products, etc., d. Strict temperature limits for these agents preventive measures cannot be given, because they vary and depend on the chemical properties of the starting material, on the catalysts possibly used and, d. The indicated malerials have resistance, especially against the influence of sulfur compounds in the presence of hydrogen in the substances entering the At temperatures above 300 - • 350 ° and under pressures, e.g. from 50 to 200 or more atmospheres, these materials also prevent the release of carbon due to the decomposition of hydrocarbons and the formation of methane. Of the materials mentioned, special attention is paid to carbon-poor alloys, in particular containing a small amount of carbon, e.g. less than 0.25%, such as steel, containing 24.2% Fe, 61.1% Ni, 11.93% Cr, 0.13% C, or Krupp V2A steel, or WT2. Since the alloy used is too brittle due to certain constituents, for example the chromium content, a certain nickel content may prove to be desirable. Like iron, which can be harmless by adding to other bodies, it is also possible to completely compensate for the damaging effects of nickel, and other components such as carbon, by adding other admixtures. It is also possible to use successfully alloys obtained in a vacuum, e.g. Heraus chromium-nickel containing 24.2% Fe, 60.1% Ni, 133.8% Cr, 0.02% C. Tungsten carbide can also be used. May speech. The metals, alloys or the like used, it is better to free, if possible, from impurities at the grain boundary, such as, for example, oxygen, sulfur, carbon, etc. This can be achieved, for example, by means of metals or alloys with ordinary properties are treated in high temperature with gases, e.g. humid hydrogen, which react with pollutants, produce volatile compounds. In this way a strong crystal structure is obtained which, especially at the surface smooth, even with high stresses of the apparatus parts covered with it or made of it, cannot be affected. PL

Claims

1. Patent claims, 1. Method for obtaining valuable liquid products from various types of coal, tar, mineral oils, their distillation products, extraction and transformation of residues and similar bodies, by means of treatment with hydrogen or containing them with gases at an elevated temperature and a pressure above 50 atm according to the main patent No. 6025, characterized by the fact that in the case of the absence of larger amounts of carbon monoxide and larger amounts of bodies in the reduction gas, leading to the formation of carbon monoxide in the reaction chamber of the reaction space, in contact with the reaction bodies and possibly with individual further parts of the apparatus, and especially with parts which, at a temperature above 300 ° C, come into contact with products containing sulfur or hydrocarbons, the harmful iron, nickel and copper are removed, these the last one only in the presence of sulfur, 2, The method according to claim 1, characterized by the fact that the reaction space or other parts of the These apparatus are covered with or made of aluminum or alloys containing it, chromium or molybdenum, or tungsten, or vanadium, or alloys containing chrame, cobalt, molybdenum, tungsten, vanadium, manganese, or several of these elements, possibly with greater nickel content and low carbon content, or carbons of refractory metals, especially metals belonging to groups 5 and 6 of the periodic system, 3. 1 - 2, which means that the alloys obtained by vacuum melting are used, 4, The method according to claims 1 and 3, characterized in that the metals used, the alloys and t, d, are free from impurities in far-reaching degree. 5, The method according to claim 1, characterized in that in the absence of sulfur, copper, silver or their alloys or materials that behave similarly are used, I, G. Farbenindustrie Aktiengesellschaft, Zastepca: M. Skrzypkowski, patent attorney. Print by L. Boguslawski, Warsaw. PL