LU85487A1 - PROCESS FOR PURIFYING LIQUID HYDROCARBON FEEDSTOCKS - Google Patents
PROCESS FOR PURIFYING LIQUID HYDROCARBON FEEDSTOCKS Download PDFInfo
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- LU85487A1 LU85487A1 LU85487A LU85487A LU85487A1 LU 85487 A1 LU85487 A1 LU 85487A1 LU 85487 A LU85487 A LU 85487A LU 85487 A LU85487 A LU 85487A LU 85487 A1 LU85487 A1 LU 85487A1
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- Luxembourg
- Prior art keywords
- nickel
- charge
- absorbent material
- weight
- liquid
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- 239000007788 liquid Substances 0.000 title claims description 28
- 229930195733 hydrocarbon Natural products 0.000 title claims description 27
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 27
- 238000000034 method Methods 0.000 title claims description 17
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 58
- 229910052759 nickel Inorganic materials 0.000 claims description 25
- 239000002250 absorbent Substances 0.000 claims description 21
- 230000002745 absorbent Effects 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 17
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 17
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims description 16
- 238000000746 purification Methods 0.000 claims description 8
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 claims 1
- 150000001247 metal acetylides Chemical class 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- -1 silico-aluminas Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Gas Separation By Absorption (AREA)
Description
F 523F 523
PROCEDE POUR ENLEVER LE SULFURE DE CARBONYLE DES CHARGES D'HYDROCARBURES LIQUIDESPROCESS FOR REMOVING CARBONYL SULFIDE FROM LIQUID HYDROCARBON FEEDSTOCKS
La présente invention se rapporte à un procédé pour enlever le soufre présent sous forme d'oxysulfure de carbone ou sulfure de carbonyle,. hors d'hydrocarbures liquides, en particulier les charges d'hydrocarbures contenant no tamment du propylène.The present invention relates to a process for removing the sulfur present in the form of carbon oxysulfide or carbonyl sulfide. excluding liquid hydrocarbons, in particular charges of hydrocarbons containing in particular propylene.
Dans les raffineries, le traitement des hydrocarbures liquides pour l'enlèvement ou pour la transformation des impuretés nécessite des procédés complexes et coûteux. Les divers composés sulfurés représentent les impuretés habituelles que l'on cherche à éliminer. Ceux-ci soot l'acide suifhydrique,les mercaptans et en particulier le sulfure de carbonyle.In refineries, the treatment of liquid hydrocarbons for the removal or for the transformation of impurities requires complex and costly processes. The various sulfur compounds represent the usual impurities which one seeks to eliminate. These are hydrofluoric acid, mercaptans and in particular carbonyl sulfide.
La pratique qui prévaut dans l'industrie consiste à réduire la teneur en soufre en traitant les hydrocarbures à l'état gazeux. Une pratique largement acceptée consiste à enlever les sulfures hors de gaz combustibles pris à l'état gazeux avec la diéthanolamine, la diisopropanolamine, la monoéthanol-amine, et du tétraéthylène glycol. ~On sait également que ces solvants peuvent être utilisés pour'traiter les hydrocarbures à i l'état liquide.The prevailing industry practice is to reduce the sulfur content by treating the gaseous hydrocarbons. A widely accepted practice is to remove sulfides from combustible gases taken in a gaseous state with diethanolamine, diisopropanolamine, monoethanolamine, and tetraethylene glycol. ~ We also know that these solvents can be used to treat hydrocarbons in the liquid state.
Cependant, lorsque ces solvants sont utilisés pour extraire les impuretés hors d'hydrocarbures à l'état liquide, ils ne permettent pas de réduire la teneur en sulfure de carbonyle, ci-après dénommé COS pour la facilité, à moins de 5 ppm.However, when these solvents are used to extract the impurities from hydrocarbons in the liquid state, they do not make it possible to reduce the content of carbonyl sulfide, hereinafter referred to as COS for ease, to less than 5 ppm.
Or il est connu également que les nouveaux procédés de polymérisation de propylène font appel à des catalyseurs de plus en plus performants. Ces derniers, en contre-partie, sont extrêmement sensibles à toutes impuretés polaires comme par ex- 3¾ - 2 - emple le COS, dont le moment dipolaire est de 0,736 Debye.However, it is also known that new propylene polymerization processes use increasingly efficient catalysts. The latter, in return, are extremely sensitive to all polar impurities such as for example 3¾ - 2 - ample COS, whose dipole moment is 0.736 Debye.
Lorsque l'on utilise ces procédés de polymérisation, il est donc important de purifier la charge de sorte que la teneur résiduelle en impuretés soit extrêmement faible.When using these polymerization processes, it is therefore important to purify the feed so that the residual content of impurities is extremely low.
Or, avec les procédés classiques qui traitent des charges qui peuvent contenir au départ de 30 à 70 ppm de COS,on parvient à atteindre une teneur résiduelle en COS après purification de l'ordre de 10 à 20 'ppm.However, with the conventional methods which treat fillers which may contain from 30 to 70 ppm of COS at the start, it is possible to reach a residual COS content after purification of the order of 10 to 20 ppm.
On a déjà proposé de traiter des charges d'hydrocarbures liquides, contenant notamment du propylène, avec du 2-(2-aminoéthoxy)éthanol, connu sous le nom de diglycolamine, pour enlever le COS; cependant, la teneur résiduelle obtenue, bien que faible puisque de l'ordre du ppm, n'est pas encore suffisante pour satisfaire .les conditions des polymérisations à l'aide des catalyseurs de type Ziegler très actifs.It has already been proposed to treat loads of liquid hydrocarbons, in particular containing propylene, with 2- (2-aminoethoxy) ethanol, known under the name of diglycolamine, to remove COS; however, the residual content obtained, although low since of the order of ppm, is not yet sufficient to satisfy the conditions for the polymerizations using very active Ziegler type catalysts.
A côté de la technique de traitement faisant appel à des contacts liquide-liquide, on a déjà proposé également des traitements par contacts liquide-solide.In addition to the treatment technique using liquid-liquid contacts, treatments have already been proposed by liquid-solid contacts.
Ce type de traitement a l'avantage de limiter les risques de contamination du propylène qui doit être polymérisé ultérieurement, contamination qui entraînerait la nécessité d'un second absorbeur.This type of treatment has the advantage of limiting the risks of contamination of the propylene which must be polymerized subsequently, contamination which would entail the need for a second absorber.
Ainsi, on a déjà proposé d'utiliser un matériau solide constitué d'un support inerte poreux présentant une grande surface spécifique tel que silicagel, pierre ponce ou silicate de Mg et des oxydes de Cd, Zn, Ni et Co sur lequel on fait passer la charge liquéfiée conduisant à une teneur résiduelle en , COS de la charge inférieure à 1 ppm.Thus, it has already been proposed to use a solid material consisting of an inert porous support having a large specific surface such as silica gel, pumice stone or Mg silicate and oxides of Cd, Zn, Ni and Co over which we pass the liquefied charge resulting in a residual content of COS of the charge of less than 1 ppm.
On a également proposé d'utiliser des absorbants composés d'oxyde de fer, d'oxyde de cuivre ou d'oxyde de cuivre et chrome sur un support à haute surface spécifique comme le charbon actif ou de l'alumine, de manière à réduire la teneur en COS des hydrocarbures liquides depuis 50-60 ppm dans la charge initiale jusqu'à environ 0,5 ppm.It has also been proposed to use absorbents composed of iron oxide, copper oxide or copper and chromium oxide on a support with a high specific surface such as activated carbon or alumina, so as to reduce the COS content of liquid hydrocarbons from 50-60 ppm in the initial charge up to approximately 0.5 ppm.
Cependant, bien que cette teneur soit déjà très faible, » - 3 - cela n'est pas encore suffisant pour pouvoir envoyer le propylène ainsi purifié à l'unité de polymérisation utilisant les " catalyseurs Ziegler très actifs.However, although this content is already very low, this is not yet sufficient to be able to send the propylene thus purified to the polymerization unit using the "very active Ziegler catalysts".
On a aussi proposé de traiter ces charges en les faisant passer sur des résines basiques échangeuses d'ions, à la température ambiante. Cependant, la teneur résiduelle en COS obtenue est également de l'ordre du ppm, ce qui est trop élevé pour effectuer la polymérisation en présence de catalyseurs de polymérisation de la dernière génération.It has also been proposed to treat these charges by passing them over basic ion exchange resins, at ambient temperature. However, the residual COS content obtained is also of the order of ppm, which is too high to carry out the polymerization in the presence of latest generation polymerization catalysts.
On a également proposé d'utiliser de l'oxyde de zinc déposé sur un support d'alumine, cependant ce type de catalyseur n'est pas suffisamment actif pour pouvoir enlever le COS jusqu'à obtenir des teneurs résiduelles inférieures à 30 ppb.It has also been proposed to use zinc oxide deposited on an alumina support, however this type of catalyst is not sufficiently active to be able to remove the COS until residual contents lower than 30 ppb are obtained.
Il existe dès lors un besoin pour un procédé qui permette de désulfurer et en particulier qui permette d'enlever le COS des charges d'hydrocarbures liquides oléfiniques contenant notamment du propylène et d'autres oléfines, jusqu'à ce que la teneur résiduelle en COS ne dépasse pas 30 ppb, de manière à ce que les catalyseurs de polymérisation du propylène de la nou-velle génération ne soient pas trop rapidement empoisonnés.There is therefore a need for a process which makes it possible to desulfurize and in particular which makes it possible to remove COS from the charges of olefinic liquid hydrocarbons containing in particular propylene and other olefins, until the residual COS content does not exceed 30 ppb, so that the new generation propylene polymerization catalysts are not poisoned too quickly.
La présente invention a pour but un procédé de purification des charges d'hydrocarbures liquides oléfiniques qui permette de satisfaire les critères énoncés ci-dessus.The object of the present invention is to provide a process for the purification of olefinic liquid hydrocarbon charges which makes it possible to satisfy the criteria set out above.
La présente invention a pour objet un procédé de purification qui permette d'enlever le COS des charges d'hydrocarbures liquides oléfiniques contenant notamment du propylène, -jusqu'à obtenir une teneur résiduelle en COS inférieure à 30ppb.The subject of the present invention is a purification process which makes it possible to remove the COS from the charges of olefinic liquid hydrocarbons containing in particular propylene, up to obtaining a residual COS content of less than 30 ppm.
Le procédé de purification de la présente invention pour enlever le COS des charges d'hydrocarbures liquides comprenant notamment du propylène et contenant de 1 à 70 ppm de COS, est caractérisé en ce que l'on fait passer la charge d'hydrocarbures liquides sur un matériau absorbant comprenant" du nickel déposé sur un support, le nickel étant présent sous forme d'oxyde de nickel et sous forme de nickel métallique, la quantité de nickel métallique étant comprise entre 35 et 70¾ en poids du nickel total.The purification process of the present invention for removing COS from feeds of liquid hydrocarbons comprising in particular propylene and containing from 1 to 70 ppm of COS, is characterized in that the feed of liquid hydrocarbons is passed over a absorbent material comprising "nickel deposited on a support, the nickel being present in the form of nickel oxide and in the form of metallic nickel, the amount of metallic nickel being between 35 and 70% by weight of the total nickel.
- 4 -- 4 -
On a trouvé, de manière inattendue, qu'en faisant passer une charge d'hydrocarbures liquides, en l'occurence une charge de propylène destiné à la polymérisation,sur un matériau absorbant constitué par 40 à 70 % en poids de nickel déposé sur un support représentant 60 à 30 % en poids en matériau absorbant, le nickel étant présent pour 35 à 70 % en poids sous forme de nickel métallique, on obtient une charge purifiée répondant aux conditions de pureté exigées pour une polymérisation en présence de catalyseur Ziegler de la dernière génération, c'est-à-dire notamment une teneur en COS ne dépassant pas 30 ppb.It has been found, unexpectedly, that by passing a charge of liquid hydrocarbons, in this case a charge of propylene intended for polymerization, over an absorbent material consisting of 40 to 70% by weight of nickel deposited on a support representing 60 to 30% by weight of absorbent material, nickel being present for 35 to 70% by weight in the form of metallic nickel, a purified filler is obtained which meets the purity conditions required for polymerization in the presence of Ziegler catalyst of the latest generation, that is to say in particular a COS content not exceeding 30 ppb.
Comme support sur lequel on dépose le nickel, on peut utiliser la silice, les silico-alumines, l'alumine, le kieselguhr et autres analogues.As the support on which the nickel is deposited, it is possible to use silica, silico-aluminas, alumina, kieselguhr and the like.
Le nickel peut être déposé sur le support par toutes méthodes bien connues de l'homme de l'art, par exemple, en dissolvant du nitrate de nickel dans l'eau, en mélangeant la solution avec le support et en précipitant le nickel, par exemple sous forme de carbonate de nickel, et ensuite en lavant,séchant et calcinant le précipité. Ensuite, on réduit partiellement le nickel ainsi déposé au moyen d'hydrogène de manière à former du nickel métallique en une quantité comprise entre 35 et 70 % de la quantité totale de nickel déposé, le reste étant sous forme d'oxyde de nickel.Nickel can be deposited on the support by any method well known to those skilled in the art, for example, by dissolving nickel nitrate in water, mixing the solution with the support and precipitating the nickel, by example in the form of nickel carbonate, and then by washing, drying and calcining the precipitate. Then, the nickel thus deposited is partially reduced by means of hydrogen so as to form metallic nickel in an amount between 35 and 70% of the total amount of nickel deposited, the rest being in the form of nickel oxide.
Généralement, la taille des cristallites de nickelGenerally the size of nickel crystallites
OO
après réduction est comprise entre environ 10 et 200 A. Laafter reduction is between approximately 10 and 200 A. The
*T* T
taille clés cristallites de nickel dépend entre autres de la réduction qui est effectuée. En effet, si l'on augmente le degré de réduction, on accroît la taille des cristallites mais le matériau absorbant obtenu ne présente plus d'aussi bonnes propriétés. Par contre, si on n'effectue qu'une réduction à un trop faible degré, on reste dans de bonnes dimensions pour la taille des cristallites, mais dans ce cas, la quantité de nickel disponible est trop faible pour assurer la purification de la charge avec succès.The size of the nickel crystallites depends, among other things, on the reduction that is carried out. In fact, if the degree of reduction is increased, the size of the crystallites is increased, but the absorbent material obtained no longer exhibits such good properties. On the other hand, if only a reduction is carried out to a too low degree, one remains in good dimensions for the size of the crystallites, but in this case, the quantity of nickel available is too small to ensure the purification of the charge. with success.
La surface spécifique du matériau absorbant obtenu - 5 - après réduction est généralement comprise entre 100 et 200 m^g.The specific surface of the absorbent material obtained after reduction is generally between 100 and 200 m ^ g.
La taille des particules du matériau absorbant dépend notamment de la perte de charge admise dans le réacteur; mais on a remarqué qu'il était avantageux d'uiliser le matériau absorbant sous forme finement divisée. Généralement, la dimension des particules de ce matériau ne dépassera pas environ 3 mm et sera comprise le plus souvent entre 1 et 2,5 mm.The particle size of the absorbent material depends in particular on the pressure drop admitted into the reactor; but it has been noted that it is advantageous to use the absorbent material in finely divided form. Generally, the particle size of this material will not exceed approximately 3 mm and will most often be between 1 and 2.5 mm.
Généralement, on traite des charges d'hydrocarbures liquides contenant pous de 75 % de propylène,plus particulièrement des charges contenant jusqu'à 85 et 99 % de propylène, la teneur en COS étant généralement de l'ordre de 1 à 10 ppm.Generally, liquid hydrocarbon feeds containing 75% propylene are treated, more particularly feeds containing up to 85 and 99% propylene, the COS content generally being of the order of 1 to 10 ppm.
Lorsque l'on doit traiter des charges ayant une teneur plus élevée en COS, c'est-à-dire jusqu'à 500 ppm, on leur fait d'abord subir un traitement avec un solvant aminé, comme la monoéthanolamine, de manière à réduire le taux de COS à une valeur convenable, soit moins de 70 ppm..When feedstocks having a higher COS content, i.e. up to 500 ppm, have to be treated, they are first subjected to a treatment with an amino solvent, such as monoethanolamine, so as to reduce the SOC level to a suitable value, less than 70 ppm.
Selon un mode d'exécution du procédé de la présente invention, on fait passer la charge d'hydrocarbures liquides contenant du propylène sur le matériau absorbant de la présente invention, à une température comprise généralement entre 0°C et 90eC et à une pression suffisante pour maintenir le milieu en phase liquide.According to an embodiment of the process of the present invention, the charge of liquid hydrocarbons containing propylene is passed over the absorbent material of the present invention, at a temperature generally between 0 ° C. and 90 ° C. and at a sufficient pressure. to maintain the medium in liquid phase.
La vitesse spatiale horaire de liquide ou LHSV, à laquelle on fait passer la charge, est généralement comprise entre 0,1 et 20, et de préférence comprise entre 0,2 et 15.The hourly liquid space velocity or LHSV, at which the charge is passed, is generally between 0.1 and 20, and preferably between 0.2 and 15.
Les exemples suivants sont donnés afin de mieux illustrer _le_._procédé de la présente invention, mais sans pour autant en limiter la portée.The following examples are given to better illustrate the process of the present invention, but without limiting its scope.
Exemple 1Example 1
On a fait passer une charge d'hydrocarbures liquides contenant 99 % de propylène et ayant une teneur résiduelle en COS de 2,7 ppm sur un matériau absorbant constitué par 43,3 % en poids de silice comme support, sur lequel on a déposé du nickel qui est présent sous forme de NiO pour 34 % en poids et sous forme de Ni métallique pour 22.7 % en poids.A charge of liquid hydrocarbons containing 99% propylene and having a residual COS content of 2.7 ppm was passed over an absorbent material consisting of 43.3% by weight of silica as support, on which was deposited nickel which is present in the form of NiO for 34% by weight and in the form of metallic Ni for 22.7% by weight.
Avant réduction, le matériau absorbant contenait envi-_Before reduction, the absorbent material contained about _
Claims (8)
Priority Applications (18)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| LU85487A LU85487A1 (en) | 1984-07-27 | 1984-07-27 | PROCESS FOR PURIFYING LIQUID HYDROCARBON FEEDSTOCKS |
| BE0/215384A BE902942A (en) | 1984-07-27 | 1985-07-19 | PROCESS FOR REMOVING CARBONYL SULFIDE FROM LIQUID HYDROCARBON FEEDSTOCKS. |
| GB08518304A GB2162194B (en) | 1984-07-27 | 1985-07-19 | Process for removing carbonyl sulphide from liquid hydro-carbon feedstocks |
| IT21650/85A IT1187696B (en) | 1984-07-27 | 1985-07-19 | PROCEDURE FOR REMOVING CARBONYL SULPHIDE FROM LIQUID HYDROCARBON CHARGES |
| DE3526153A DE3526153C2 (en) | 1984-07-27 | 1985-07-22 | Process for removing carbonyl sulfide from liquid hydrocarbon feeds |
| NL8502109A NL194334C (en) | 1984-07-27 | 1985-07-23 | Process for removing carbonyl sulfide from a liquid hydrocarbon starting material. |
| FR8511344A FR2568262B1 (en) | 1984-07-27 | 1985-07-24 | PROCESS FOR REMOVING CARBONYL SULFIDE FROM LIQUID HYDROCARBON FEEDSTOCKS |
| NO852939A NO173782C (en) | 1984-07-27 | 1985-07-24 | Procedure for Removing Carbonyl Sulfide from Liquid Hydrocarbons |
| AU45358/85A AU4535885A (en) | 1984-07-27 | 1985-07-25 | Process for removing carbonyl-sulfide from liquid hydrocarbon feedstocks |
| JP60165615A JPS6176425A (en) | 1984-07-27 | 1985-07-26 | Removal of carbonyl sulfide from liquid hydrocarbon supplying raw material |
| PT80877A PT80877B (en) | 1984-07-27 | 1985-07-26 | PROCESS FOR THE ELIMINATION OF CARBONYL SULFIDE FROM LIQUID HYDROCARBON LOADS |
| MX206114A MX168045B (en) | 1984-07-27 | 1985-07-26 | PROCESS FOR REMOVING CARBONYL SULFIDE FROM CARGO MATERIALS |
| ES545570A ES8608463A1 (en) | 1984-07-27 | 1985-07-26 | Process for removing carbonyl sulphide from liquid hydro-carbon feedstocks |
| AT2221/85A AT393132B (en) | 1984-07-27 | 1985-07-26 | METHOD FOR REMOVING CARBONYL SULFIDE FROM LIQUID HYDROCARBON OUTPUT MATERIALS |
| SU853932563A SU1447274A3 (en) | 1984-07-27 | 1985-07-26 | Method of cleaning liquid hydrocarbon charge |
| KR1019850005461A KR930011063B1 (en) | 1984-07-27 | 1985-07-27 | Removal of Carbonyl Sulfide from Liquid Hydrocarbon Feedstocks |
| CN 85105770 CN1006804B (en) | 1984-07-27 | 1985-07-29 | Process for removing carbonyl sulfide from liquid hydrocarbon feedstocks |
| US08/071,435 US5470456A (en) | 1984-07-27 | 1993-06-01 | Process for removing carbonyl-sulfide from liquid hydrocarbon feedstocks |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| LU85487 | 1984-07-27 | ||
| LU85487A LU85487A1 (en) | 1984-07-27 | 1984-07-27 | PROCESS FOR PURIFYING LIQUID HYDROCARBON FEEDSTOCKS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| LU85487A1 true LU85487A1 (en) | 1986-02-12 |
Family
ID=19730298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| LU85487A LU85487A1 (en) | 1984-07-27 | 1984-07-27 | PROCESS FOR PURIFYING LIQUID HYDROCARBON FEEDSTOCKS |
Country Status (16)
| Country | Link |
|---|---|
| JP (1) | JPS6176425A (en) |
| KR (1) | KR930011063B1 (en) |
| AT (1) | AT393132B (en) |
| AU (1) | AU4535885A (en) |
| BE (1) | BE902942A (en) |
| DE (1) | DE3526153C2 (en) |
| ES (1) | ES8608463A1 (en) |
| FR (1) | FR2568262B1 (en) |
| GB (1) | GB2162194B (en) |
| IT (1) | IT1187696B (en) |
| LU (1) | LU85487A1 (en) |
| MX (1) | MX168045B (en) |
| NL (1) | NL194334C (en) |
| NO (1) | NO173782C (en) |
| PT (1) | PT80877B (en) |
| SU (1) | SU1447274A3 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2619120B1 (en) * | 1987-08-07 | 1989-12-29 | Inst Francais Du Petrole | PROCESS FOR THE JOINT REMOVAL OF ARSENIC AND CARBON OXYSULFIDE FROM A CUP OF LIQUID PHASE UNSATURATED HYDROCARBONS |
| ATE73118T1 (en) * | 1987-09-24 | 1992-03-15 | Fina Research | PROCESS FOR REMOVAL OF ARSININE FROM LIGHT OLEFIN CONTAINING HYDROCARBON FEEDS. |
| BE1004214A3 (en) * | 1990-03-23 | 1992-10-13 | Fina Research | Process to remove loads of hydride antimony oil liquids |
| AU663056B2 (en) * | 1990-07-27 | 1995-09-28 | Exxon Chemical Patents Inc. | Hydrocarbon treatment |
| DE69318403T2 (en) * | 1993-09-15 | 1998-10-01 | Fina Research | Process for the polymerization of olefins |
| DE69309680T2 (en) * | 1993-09-20 | 1997-08-21 | Fina Research | Process for removing arsenic and carbonyl sulfide from light olefins containing hydrocarbon feeds |
| CA2149724A1 (en) | 1994-05-19 | 1995-11-20 | Yoshinao Ito | Method for purification of .alpha. olefins for polymerization use and methd for production of poly-.alpha.-olefins |
| CN102643154A (en) * | 2003-09-23 | 2012-08-22 | 英格哈得公司 | Process for the removal of sulfur compounds from hydrocarbon feedstocks |
| US8323603B2 (en) | 2004-09-01 | 2012-12-04 | Sud-Chemie Inc. | Desulfurization system and method for desulfurizing a fuel stream |
| US7780846B2 (en) | 2004-09-01 | 2010-08-24 | Sud-Chemie Inc. | Sulfur adsorbent, desulfurization system and method for desulfurizing |
| EP2006011A1 (en) * | 2007-06-22 | 2008-12-24 | Total Petrochemicals Research Feluy | Process for reducing carbon monoxide in olefin-containing hydrocarbon feedstocks |
| EP2006012A1 (en) * | 2007-06-22 | 2008-12-24 | Total Petrochemicals Research Feluy | Process for the polymerisation of olefins |
| EP2199269A1 (en) | 2008-12-22 | 2010-06-23 | Total Petrochemicals Research Feluy | Method to purify olefin-containing hydrocarbon feedstocks |
| DE102012212316A1 (en) * | 2012-07-13 | 2014-01-16 | Evonik Industries Ag | Sulfur adsorption before oligomerization plants |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE636323A (en) * | ||||
| US2756182A (en) * | 1955-01-12 | 1956-07-24 | Exxon Research Engineering Co | Desulfurization of hydrocarbons with an iron group carbonyl impregnated on an adsorbent |
| FR1483583A (en) * | 1965-06-19 | 1967-06-02 | Basf Ag | Process for the removal of carbon oxysulfide from liquid hydrocarbon mixtures |
| GB1240134A (en) * | 1968-11-27 | 1971-07-21 | British Petroleum Co | Desulphurisation process |
| DE2447910A1 (en) * | 1974-10-08 | 1976-04-22 | Basf Ag | Removal of sulphur cpds from gaseous of liquid hydrocarbons - by contact with basic carbonates of transition metals, reduced in hydrogen |
| LU85309A1 (en) * | 1984-04-13 | 1985-11-27 | Labofina Sa | PROCESS FOR REMOVING CARBONYL SULFIDE FROM LIQUID HYDROCARBON FEEDSTOCKS |
-
1984
- 1984-07-27 LU LU85487A patent/LU85487A1/en unknown
-
1985
- 1985-07-19 BE BE0/215384A patent/BE902942A/en not_active IP Right Cessation
- 1985-07-19 GB GB08518304A patent/GB2162194B/en not_active Expired
- 1985-07-19 IT IT21650/85A patent/IT1187696B/en active
- 1985-07-22 DE DE3526153A patent/DE3526153C2/en not_active Expired - Fee Related
- 1985-07-23 NL NL8502109A patent/NL194334C/en not_active IP Right Cessation
- 1985-07-24 NO NO852939A patent/NO173782C/en not_active IP Right Cessation
- 1985-07-24 FR FR8511344A patent/FR2568262B1/en not_active Expired
- 1985-07-25 AU AU45358/85A patent/AU4535885A/en not_active Abandoned
- 1985-07-26 ES ES545570A patent/ES8608463A1/en not_active Expired
- 1985-07-26 MX MX206114A patent/MX168045B/en unknown
- 1985-07-26 AT AT2221/85A patent/AT393132B/en not_active IP Right Cessation
- 1985-07-26 JP JP60165615A patent/JPS6176425A/en active Granted
- 1985-07-26 PT PT80877A patent/PT80877B/en not_active IP Right Cessation
- 1985-07-26 SU SU853932563A patent/SU1447274A3/en active
- 1985-07-27 KR KR1019850005461A patent/KR930011063B1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| PT80877B (en) | 1987-11-30 |
| NO173782C (en) | 1994-02-02 |
| GB8518304D0 (en) | 1985-08-29 |
| NL194334B (en) | 2001-09-03 |
| AU4535885A (en) | 1986-01-30 |
| NO173782B (en) | 1993-10-25 |
| FR2568262B1 (en) | 1988-04-01 |
| IT8521650A0 (en) | 1985-07-19 |
| ES545570A0 (en) | 1986-07-16 |
| NL8502109A (en) | 1986-02-17 |
| PT80877A (en) | 1985-08-01 |
| GB2162194A (en) | 1986-01-29 |
| SU1447274A3 (en) | 1988-12-23 |
| ES8608463A1 (en) | 1986-07-16 |
| JPH0552294B2 (en) | 1993-08-05 |
| NL194334C (en) | 2002-01-04 |
| NO852939L (en) | 1986-01-28 |
| FR2568262A1 (en) | 1986-01-31 |
| KR860001177A (en) | 1986-02-24 |
| IT1187696B (en) | 1987-12-23 |
| MX168045B (en) | 1993-04-29 |
| ATA222185A (en) | 1991-01-15 |
| GB2162194B (en) | 1988-05-05 |
| BE902942A (en) | 1986-01-20 |
| DE3526153A1 (en) | 1986-01-30 |
| KR930011063B1 (en) | 1993-11-20 |
| DE3526153C2 (en) | 1995-03-09 |
| AT393132B (en) | 1991-08-26 |
| JPS6176425A (en) | 1986-04-18 |
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