KR840007891A - Decomposition and Hydrogenation of Refractory Petroleum Tailings Products - Google Patents

Abstract

No content.

Description

Decomposition and Hydrogenation of Refractory Petroleum Tailings Products

Since this is an open matter, no full text was included.

1 is a schematic of a recycling process in a centrifugal reactor.

2 shows a continuous process of converting various raw materials into useful products by a parallel method.

Claims (27)

Carbonaceous starting materials, such as crude oil, its tailings, and the like, containing refractory components consisting of a) -e) as reactions, were added as low viscosity products or more hydrogenated target products in the presence of alkali metal sulfide catalysts without addition of hydrogen gas. How to switch. a) carbonaceous material of natural crude oil, natural asphalt material, natural tar, pitch, gilsonite, slurry oil, solvent extraction asphaltene in the presence of water and catalyst added in the form of steam in the first stage reaction zone: pitch from coal or Tar: Petroleum tailings: Mixture of oils, resins and asphaltenes: Or oil-resin-asphaltene fraction of distillate with boiling point above 455 ° C: Distillation tailings without explosive distillation: Coal oil extract: Tetort Shale The bottoms oil of interest: the heavy bottoms material of the form of SASOL obtained from a coal vaporizer is reacted with at least one of the bottom coking products obtained by distilling the bottoms material or a mixture of the above: wherein the catalyst is an alkali metal sulfide and the starting Another decomposition catalyst for the pretreatment of the refractory components in the amorphous zone in the first reaction zone consists of at least 5%. The catalyst is present in a mixture with the alkali metal sulfide catalyst in order to treat the refractory components in the starting material, and the decomposition catalyst is a supported or unsupported catalyst composition as follows: 1) Alkali metal hydroxide is methanol, ethanol, 1- It consists of a first solution dissolved in propanol or 1-butanol or a mixture of these alkanols, and a second solution in which water containing alkali metal hydroxides is added to the alkali metal hydroxide-alkanol solution of 1) above. Wherein the alkali metal hydroxide in the solution is present in a molar number of 0.5: 1-1: 0.5, and the first or second solution is saturated with hydrogen sulfide to form i) a single commercial solution or ii) its solution. Wherein the catalyst composition comprises a single phase solution of (i), a phase solution of (ii) above, each of the phases of (ii), a mixture of phases of (ii) and (i) A mixture of a single commercial solution of), a mixture of that phase of (ii) and a single phase of (i) taken from each other. b) recovering the top product comprising gas in vapor or gaseous product state from the first stage reaction zone and separating the bottom product; c) recycling the bottom product or paralleling the bottom product from the product obtained from the first reaction zone. The product consists of a liquid product, entrained liquid product, or some pretreated refractory component of the starting material. d) reacting the bottom product separated in the presence of the first introduced steam or added steam in the presence of the decomposition catalyst as described in (a) above with the alkali metal sulfide catalyst described above and e) recovering the product produced in step (d). do. The process of claim 1 wherein step (a) and step (d) catalyst are metal supported catalysts. The process of claim 1 wherein the product of step (c) is recycled instead of being treated separately. The process of claim 1, wherein the vapor phase or gaseous tower reaction product of step (b) or step (d) is hydrogenated by reacting under support or steam addition with at least one further reaction zone after cooling or in cooling (at the support catalyst). Consisting of an alkali metal hydrogen sulfide, sulfide, polysulfide or hydrate of sulfide, hydrate of polysulfide or mixtures thereof). A method of obtaining a bromine reduced product as compared to the bromine value of the product of step (b) or (d). The process of claim 1 or 3, wherein the vaporized or gaseous top reaction product of step (b) is reacted as it is or hydrogenated by cooling under the addition of a supported catalyst and steam in at least one further reaction zone (where the supported catalyst is alkali Consisting of hydrogen sulfide, sulfide, polysulfide or hydrate of sulfide, hydrate of polysulfide, or mixtures thereof). The catalyst according to claim 1 or 5, wherein the catalyst of step (a) or step (d) consists of 1) catalyst A as support catalyst or 2) up to 95% of catalyst A (K molar basis) is catalyst B, C, Consisting of a mixture mixed with D, E or a mixture thereof, wherein each catalyst is prepared as follows: wherein catalyst A comprises 1 mole of potassium hydroxide ethanol, methane ethanol-methanol mixture, 1-propanol or 1- It is prepared by dissolving in potassium butanol and reacting this potassium hydroxide solution with hydrogen sulfide blown through the solution, recovering the catalyst mixture and then separating the alcohols from the solution: Catalyst B is about 86% potassium hydroxide for analytical or industrial purposes. Dissolve potassium hydroxide in ethanol or methanol and introduce hydrogen sulfide in the first vessel, saturate with hydrogen sulfide in a series of vessels, collect the alkanol without distilling it off, Is prepared by capturing the alkanol produced by the exothermic reaction of potassium hydroxide with hydrogen sulfide and stopping the addition of hydrogen sulfide when the last vessel containing KOH reacts: Catalyst C is heated without adding 6 moles of KOH. Dissolve in about 41 / 2-71 / 2 moles of water, add about 2-2.5 cc of methanol or ethanol per mole of KOH, and add about 4 moles of elemental sulfur: Add sulfur to make the catalyst desired sulfur. Obtained by adding an appropriate amount of sulfur to control to produce a sulfide of the formula K ₂ S _1.1 -K ₂ S ₅ : Catalyst D is dissolved in 1 mole of KOH in 1 mole of water and 2 ml of methanol or ethanol immediately after KOH is dissolved. Is prepared by obtaining a catalyst of the formula K ₂ S _1.1 -K ₂ S ₅ by adjusting the sulfur content of the formula to be desired: Catalyst E is a dry KHS powder or slurry with each of the above mentioned catalysts or catalysts A, B, C Or adding to the mixture of D, wherein the addition amount is added per mole (K ₂ S (experimental) sulfide-K ₂ S _2.5 (experimental) 1 / 5-1 / 3 mole based on the number of K moles of KHS) . The process of claim 1 wherein the catalyst of step (a) or (d) is a support catalyst and the support is a porous metal, chromium sulphate, zeolite or alumina. The method of claim 1, wherein the catalyst of step (a) or (d) is a porous support catalyst and the porous metal is stainless steel up to 35% by volume metal. The catalyst according to claim 6, wherein the carbonaceous starting material reacted in step (a) is heavy crude oil or non-boiling tailings or asphaltenes and the supported catalyst has at least 75 weight of catalyst A and the remaining catalyst D deposited on the catalyst support. How to be. 10. The process of claim 9, wherein catalyst A is about 5-80% by weight and the remainder is catalyst D. The process of claim 6 wherein the catalyst in step (d) is a porous metal supported catalyst A and the reaction temperature is 360-440 ° C. The process of claim 1 wherein the reaction is carried out in the presence of a porous metal support catalyst at a temperature of 160-600 ° C. under subatmospheric pressure to 150 psi. The process according to claim 6, wherein the catalyst used in another reaction is a catalyst A composition in which KHS is mixed up to 15% by weight, and the resulting catalyst product is deposited on a porous stainless steel support. The process of claim 1 wherein the support of the catalyst used in the reaction is protected and the support is a porous metal, spinel chromite, alumina, zeolite or mixed support. The catalyst is supported in the 14, and the support has a pore size 6Å-13000Å, preferably alumina of 350Å-900Å, oxygen it was depositing the catalyst to reach a mixture state with the alkanol of glycerol or up to C ₆ From the attack by the catalyst by calcination under exclusion or by depositing the glycerol or polyalkanol to the support followed by heating the support to 200 ° C., followed by cooling and depositing the catalyst thereon and heating the catalyst to 560 ° To protect the alumina. 2. The process of claim 1 wherein the carbonaceous material in the second reaction zone is the tailings of the first reaction zone collected in a cyclone zone maintained at 390 ° C. The process of claim 1 wherein after recovering the product from step (c), a portion of the liquid product is separated to further react in at least one second reaction zone (d) and the bottom product resulting from the zone (d) reaction is further removed. To react further in the reaction zone. The process of claim 1 wherein the reaction in steps (a) and (d) is carried out at a temperature of 560 ° C. or less. The reaction product of claim 1, wherein the overhead reaction product from step (a) is quenched immediately after step (a) and then reacted in the above-described zone and the overhead reaction product of step (d) is cooled to hydrogenate after cooling. Further reaction in another reaction zone. The process according to claim 1, wherein the reaction in step (a) or step (d) is carried out using a catalyst supported on a porous metal in a jet phase reactor fixed bed reactor, a liquid phase reactor or a fluidized bed reactor. The process according to claim 6, wherein the reaction in step (a) is carried out in a jet phase reactor using a catalyst supported on a zeolite, the catalyst consisting of 25% catalyst A and 75% catalyst A. The process according to claim 6, wherein the reaction in step (d) is carried out in a jet phase reactor wherein the catalyst is supported on a zeolite support and the catalyst is entirely of catalyst A. The reaction of claim 6, wherein the reaction in step (a) is carried out in a rotating basket or a jet phase reactor and the catalyst is a mixture of catalyst A with catalysts B, C, D or mixtures thereof and 3-95% by weight of the amount of A. And wherein said catalyst is supported on zeolite, porous metal, spinel chromite or alumina. The reaction of claim 6, wherein the reaction in step (d) is carried out in a rotating basket or eruption bed reactor, wherein the catalyst is a mixture of catalyst A with catalysts B, C, D or mixtures thereof and the amount of A is 50-100% by weight. How to be. 25. The process of claim 24, wherein catalyst A is 50-95 weight percent. 7. The process according to claim 6, wherein the column top product to be produced in the reactions (a) and (d) is further reacted before hydrogenation. 27. The method according to claim 26, wherein the column top products of steps (a) and (d) are prepared by adding catalyst A, KHS, catalyst C: catalyst B and A (B is 50% or more based on the number of moles of K) or catalyst B. Hydrogenated by. ※ Note: The disclosure is based on the initial application.