DE854213C - Process for the polymerisation of hydrocarbons - Google Patents

Process for the polymerisation of hydrocarbons

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Publication number
DE854213C
DE854213C DEB6602D DEB0006602D DE854213C DE 854213 C DE854213 C DE 854213C DE B6602 D DEB6602 D DE B6602D DE B0006602 D DEB0006602 D DE B0006602D DE 854213 C DE854213 C DE 854213C
Authority
DE
Germany
Prior art keywords
hydrocarbons
silica
polymerisation
catalysts
advantageously
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
DEB6602D
Other languages
German (de)
Inventor
Gerhard Dr Free
Wilhelm Von Dr Fuener
Kurt Dr Peters
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to DEB6602D priority Critical patent/DE854213C/en
Application granted granted Critical
Publication of DE854213C publication Critical patent/DE854213C/en
Expired legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08Catalytic processes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08Catalytic processes
    • C07C2/14Catalytic processes with inorganic acids; with salts or anhydrides of acids
    • C07C2/20Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
    • C07C2/22Metal halides; Complexes thereof with organic compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08Silica

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Description

Verfahren zur Polymerisation von Kohlenwasserstoffen Es wurde gefunden, daß man die Polymerisation von Kohlenwasserstoffen vorteilhaft in Gegenwart von Katalysatoren durchführen kann, die Kieselsäure und mindestens zwei zweckmäßig bei der Herstellung der Kieselsäure zugesetzte Metallverbindungen enthalten und bei deren Herstellung das So], aus dein die Kieselsäure als Gel abgeschieden wird, eine Wasserstoff-Ionen-Konzentration pK zwischen 3 und 7, zweckmäßig zwischen 3,5 und 6,5 besitzt. Die Durchführung der Polymerisation geschieht wie mit anderen Katalysatoren bei erhöhter Temperatur und vorzugsweise unter erhöhtem Druck. Die Temperaturen liegen im allgemeinen zwischen 130 und 27o°, vorteilhaft zwischen i8o und 23o', die Drücke zweckmäßig oberhalb 2o at, am besten zwischen 70 und 22o at. Man kann aber auch bei gewöhnlichem Druck arbeiten.Process for the polymerisation of hydrocarbons It has been found that the polymerisation of hydrocarbons can advantageously be carried out in the presence of catalysts which contain silica and at least two metal compounds expediently added in the production of the silica and in their production the so] from which the silica is used Gel is deposited, has a hydrogen ion concentration pK between 3 and 7, expediently between 3.5 and 6.5 . The polymerization is carried out as with other catalysts at elevated temperature and preferably under elevated pressure. The temperatures are generally between 130 and 27o °, advantageously between 180 and 23o, the pressures expediently above 20 atm, preferably between 70 and 220 atm. However, normal pressure can also be used.

Die in der beschriebenen Weise hergestellten Katalysatoren haben gegenüber anderen kieselsäurehaltigen Katalysatoren den Vorteil einer besonders hohen Selektivität hinsichtlich der gebildeten Erzeugnisse. d. h. von den Erzeugnissen siedet ein größerer Anteil innerhalb eines engeren Siedebereichs. Sie enthalten z. B. bei Einhaltung einer bestimmten Polymerisationstemperatur mehr Dimere des Ausgangsolefins oder bei Einhaltung einer höheren Temperatur mehr Trimere usw. als dies bei Anwendung anderer kieselsäurehaltiger Katalysatoren unter entsprechenden Bedingungen der Fall ist. Dies bedingt neben einer erhöhten Ausbeute an den eigentlich gewünschten Erzeugnissen noch den weiteren Vorteil, draß infolge der wesentlichen Verringerung der Bildung hochpolymerer Produkte, die die Katalysatorwirkung herabsetzen, die Lebensdauer der neuen Katalysatoren wesentlich länger ist, Beispiel 1,3 1 Wasserglaslösung, die 26 % Si 02 enthält, wird mit io 1 Wasser verdünnt und mit 43occm konzentrierterSalzsäureversetzt. ZudieserLösungwerden 3,95 kg Aluminiumnitrat [AI(NO3)3-9H20], 6o g Eisenchlorid (Fe C13 - 6H2.0) und 18 g Magnesiumchlorid [MgCl, # 6 H20] in io 1 Wasser gelöst zugegeben. Zu 31 Wasser, das durch Ammoniakzusatz auf das gewünschte PH von 5,5 eingestellt ist, wird unter starkem Rühren das so hergestellte klare Sol und eine 2oo/oige Ammoniaklösung so zufließen gelassen, daß in der Flüssigkeit, gemessen mit einer Antimonelektrode, der pH-Wert 5,5 dauernd aufrechterhalten bleibt. Die ausgefällte Masse wird filtriert, mit auf ph = 5,5 eingestelltem Wasser chlorfrei gewaschen und getrocknet. Über diesen Katalysator wird ein vorwiegend aus Olefinen. bestehendes Gemisch gasförmiger Kohlenwasserstoffe bei 200° und unter einem Druck von ioo at geleitet. 9o °/o der Olefine werden dabei zu flüssigen, vorwiegend unterhalb 200° siedenden Kohlenwasserstoffen umgesetzt. Die Octanzahl der bis zu i8o° siedenden Benzinfraktion ist 98 (nach der Researchmethode).The catalysts prepared in the manner described have the advantage over other silica-containing catalysts of a particularly high selectivity with regard to the products formed. ie a larger proportion of the products boils within a narrower boiling range. They contain z. B. when maintaining a certain polymerization temperature more dimers of the starting olefin or when maintaining a higher temperature more trimers, etc. than is the case when using other silica-containing catalysts under appropriate conditions. In addition to an increased yield of the actually desired products, this also results in the further advantage that, as a result of the substantial reduction in the formation of high-polymer products which reduce the catalytic effect, the life of the new catalysts is significantly longer, Example 1.3 1 waterglass solution, which is 26% Si 02 contains, is diluted with 10 l of water and treated with 43 cm of concentrated hydrochloric acid. ZudieserLösungwerden 3.95 kg of aluminum nitrate [Al (NO3) 3-9H20], 6o g ferric chloride (Fe C13 - 6H2.0) and 1 8 g of magnesium chloride [MgCl, # 6 H20] was added io dissolved in 1 water. The clear sol prepared in this way and a 2oo% ammonia solution are added to water, which has been adjusted to the desired pH of 5.5 by the addition of ammonia, with vigorous stirring so that the pH in the liquid, measured with an antimony electrode, is Value 5.5 is maintained permanently. The precipitated mass is filtered, washed free of chlorine with water adjusted to pH = 5.5 and dried. This catalyst is made up of predominantly olefins. existing mixture of gaseous hydrocarbons passed at 200 ° and under a pressure of 100 atm. 90% of the olefins are converted into liquid hydrocarbons, which predominantly boil below 200 °. The octane number of the gasoline fraction boiling up to 180 ° is 98 (according to the research method).

Claims (1)

PATENTANSPRUCH: Verfahren zur Polymerisation von Kohlenwasserstoffen, dadurch gekennzeichnet, daß man einen Katalysator verwendet, der unter Überführung eines kieselsäurehaltigen Sols bei einer Wasserstoffionenkonzentration pli zwischen 3 und 7, zweckmäßig zwischen 3,5 und 6,5, in die Gelform hergestellte Kieselsäure und mindestens zwei zweckmäßig bei der Herstellung der Kieselsäure zugesetzte Metallverbindungen enthält. Angezogene Druckschriften: Deutsche Patentschrift Nr. 571 122; französische Patentschrift Nr. 82679o; USA.-Patentschrift Nr. 2 o68 o16.PATENT CLAIM: A process for the polymerization of hydrocarbons, characterized in that a catalyst is used which converts a silicic acid-containing sol at a hydrogen ion concentration pli between 3 and 7, advantageously between 3.5 and 6.5, into the gel form of silica and at least two appropriately contains metal compounds added in the preparation of the silica. Cited publications: German Patent No. 571 122; French Patent No. 82679o; U.S. Patent No. 2,068,016.
DEB6602D 1938-12-24 1938-12-24 Process for the polymerisation of hydrocarbons Expired DE854213C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEB6602D DE854213C (en) 1938-12-24 1938-12-24 Process for the polymerisation of hydrocarbons

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEB6602D DE854213C (en) 1938-12-24 1938-12-24 Process for the polymerisation of hydrocarbons

Publications (1)

Publication Number Publication Date
DE854213C true DE854213C (en) 1952-10-30

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Family Applications (1)

Application Number Title Priority Date Filing Date
DEB6602D Expired DE854213C (en) 1938-12-24 1938-12-24 Process for the polymerisation of hydrocarbons

Country Status (1)

Country Link
DE (1) DE854213C (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE571122C (en) * 1920-02-28 1933-02-23 Silica Gel Corp Process for the production of catalytically active gels
US2068016A (en) * 1933-03-06 1937-01-19 Gen Motors Corp Method of polymerizing olefins
FR826790A (en) * 1936-10-07 1938-04-08 Standard Oil Dev Co Process for the production of liquid hydrocarbons from gaseous olefins

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE571122C (en) * 1920-02-28 1933-02-23 Silica Gel Corp Process for the production of catalytically active gels
US2068016A (en) * 1933-03-06 1937-01-19 Gen Motors Corp Method of polymerizing olefins
FR826790A (en) * 1936-10-07 1938-04-08 Standard Oil Dev Co Process for the production of liquid hydrocarbons from gaseous olefins

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