JPH04132793A - Preparation of hydrocarbon which is liquid in ordinary state - Google Patents

Abstract

PURPOSE: To produce hydrocarbon good in catalyst stability and liquid in normal state by passing a hydrocarbonaceous supply raw material containing an olefin through a reactor containing catalyst particles upwardly at a specified temp. and under a high pressure.

CONSTITUTION: A hydrocarbonaceous supply raw material containing 2-6C olefins is passed through a reactor storing catalyst particles containing a crystalline support stagnated for at least one hr under a reaction condition upwardly at a temp. from 150 to 295°C, pref., from 180 to 280°C under a high pressure to obtain objective hydrocarbon. The above mentioned catalyst pref. contains crystalline aluminosilicate (pref., ZSM-5, mordenite) and nickel.

COPYRIGHT: (C)1992,JPO

Description

[Detailed description of the invention]

[0001]

[Industrial application field]

The present invention relates to a process for producing normally liquid hydrocarbons from hydrocarbonaceous feedstocks comprising olefins containing 2 to 6 carbon atoms, as well as to hydrocarbons obtained by a slag process. [0002]

[Conventional technology]

A process for the conversion and catalytic reformation of light olefin gases by contacting the feedstock with a fluidized bed of zeolite catalysts at temperatures between 316 and 399°C is described in U.S. Pat.
, 827,069. The fluidized bed is maintained by passing feed vapor upwardly through the fluidized catalyst bed under turbulent conditions. The coked catalyst is continuously removed from the reaction zone and oxidatively regenerated, and the regenerated catalyst is returned to the reaction zone. An olefin oligomerization process carried out using a slurry containing a catalyst comprising an amorphous solid catalyst support is described in South African Patent Specification No. 892236. Olefinic hydrocarbons are heated to temperatures ranging from 0 to 450°C and pressures ranging from about 1 to about 200 atmospheres using a catalyst comprising a crystalline aluminosilicate chemically combined with subaluminum fluoride or subsilicon fluoride. A method for polymerization is described in U.S. Pat. No. 3,515,769. [0003]

[Solutions of the invention]

passing the feed upward at a temperature of 150 to 295°C through a reactor containing catalyst particles comprising a crystalline support, the catalyst particles remaining in the reactor for at least 1 hour under reaction conditions; It has now surprisingly been found that good catalyst stability can be achieved by -layers. - Better catalyst stability means that the desired conversion level can be achieved for a longer time. Furthermore, the exothermic heat generated in the Gagaru method can be removed more easily.
That's what I understand. [0004]

[Means for solving the invention]

The invention therefore provides catalyst particles comprising an olefin containing 2 to 6 carbon atoms remaining in a reactor for at least 1 hour under charcoal, said catalyst particles comprising a crystalline support. of the feedstock to a reactor containing 150 to 29
The process is characterized in that it is passed upward at a temperature of 5° C. and high pressure. The method preferably operates at a temperature of 180°C to 295°C.
The layering is preferably carried out at a temperature of 180 DEG to 280 DEG C. Furthermore, the method preferably operates at a pressure of 2 to 100 bar, preferably 10 to 50 bar and preferably 0.5 bar. 1~
10 kg feed/kg catalyst/hour-layer preferably from 0.2 to
It is carried out at a space velocity of 5 kg feed/kg catalyst/hour. [0005] In the process according to the invention, the feedstock is passed upwardly into the reactor. It is understood that it will be introduced in Different types of catalyst beds can be used in the process, such as fixed beds or fluidized beds. Fixed bed is understood to be a catalyst bed in which the catalyst volume density in the catalyst bed is between 0.45 and 0.70;
The catalyst volume density is thus the volume fraction that the catalyst particles occupy in the catalyst bed without taking into account the internal pore volume of the catalyst particles. - Layer Preferably, the fixed bed has a catalyst volume density of 0.50 to 0.65. A fluidized bed is understood to be a catalyst bed with a catalyst volume density of 0.35 to 0.50. Preferably, for reasons of process economics, the process is carried out on a fixed bed of catalyst particles. The method according to the invention preferably comprises the formation of substantial bubbles (
(e.g. in pulsed flow)) is carried out under process conditions such that the process is prevented. The description of pulse flow is from “J, Chem, Eng Japan (J, Chem, Eng
, Japan), Volume 12, Page 296, 197
It was written in 9J's Tsukushima and Kusaka articles. [0006] Suitably used catalysts include Groups 1b and 2 of the Periodic Table of Elements.
Group a, Group 2b, Group 4b, Group 5b, Group 6b, Group 7
It comprises a crystalline refractory oxide optionally containing a metal selected from Group B and Group 8 metals, preferably Group 8 metals such as nickel. A crystalline support is understood to have atoms or molecules arranged in a regularly ordered structure as observed by diffraction techniques. Preferably, the catalyst contains a crystalline aluminosilicate. Suitable refractory oxides include faujasite, zeolite, ferrierite, mordenite, zeolite beta, ZSM-5.
, ZSM-8, ZSM-11, ZSM-12, ZSM-
20, ZsM-21 and ZSM-35. Most suitably ZSM-5 and/or mordenite are applied. The following compounds may be suitably used as catalysts. That is,
The amount of metal present on the optionally nickel-hydrogen form mordenite and/or the optionally nickel-hydrogen form ZSM-5 catalyst is 20% based on the amount of refractory oxide.
% by weight (%W), suitably from 0.1 to 20%
Wt is preferably 0.1 to 10% wt. The catalyst further has a content of 10 to 8 based on the total amount of catalyst including the binder.
It may contain an amount of binder, such as alumina, in the range 0% by weight. [0007] Due to the fact that improved catalyst stability is obtained in the method according to the present invention, the catalyst does not require continuous regeneration. Therefore, the catalyst particles may remain in the reactor under the reaction conditions for at least 1 hour, suitably more than 10 hours, preferably more than 100 hours. A variety of olefinic hydrocarbons containing from 2 to 6 carbon atoms can be used in the process of the invention. Preferably, the feedstock consists of more than 50% by weight of olefins containing 2 to 6 carbon atoms such as edene, propene, n-butene, isobutene n-pentene, isopentene, n-hexene and inhexene. In addition to these olefins, hydrocarbons such as monoolefins and (cyclic) paraffins having more than 6 carbon atoms per molecule may be present in the feedstock. [0008] Particular preference is given to feedstocks containing propene and/or butenes, which are suitably obtained in (fluid) catalytic cranking processes, thermal cranking processes, coking and/or pyrolysis processes. A feedstock suitable for the present process may also be produced starting from syngas, whereby the syngas is first converted to methanol and then a product consisting essentially of olefins containing from 2 to 6 carbon atoms. converted into things. Instead, in addition to synthesis, it can be converted into products containing significant amounts of olefins containing 2 to 6 carbon atoms. [0009] The expression "normally liquid hydrocarbon" as produced in the process according to the invention means a hydrocarbon that is in the liquid phase at a temperature of 15° C. and atmospheric pressure. For such liquid hydrocarbons, in the gasoline range (40-150°C),
in the medium distillate range (kerosene and gas oil fractions boiling at 150-370°C) and in the lubricating base oil range (370°C
Exceeds ℃. ). A portion of the product obtained in the process, such as the product boiling below the gasoline boiling range and the unconverted feedstock (if any), is separated from the normally liquid product and combined with the feedstock. It can then be passed through the reactor again. Furthermore, the feedstock is treated according to the invention and the resulting effluent is divided into at least two fractions (at least one of these fractions being added to the feedstock) as described in European patent application no. having a boiling range higher than that of the olefins present in the feedstock),
Preferably, at least a portion of such fraction is then recycled to the process. The portion of the cut recycled to the first stage may be a relatively light portion or a relatively heavy portion. [0010]

【Example】

The method according to the invention is illustrated by the following example. Example ■ The amount of nickel present in hydrogen-type mordenite containing nickel is 11.0% based on the amount of mordenite.
50% wt butene and 50% wt butane in a reactor containing a catalyst that further contains 5% wt nickel) and 20% wt alumina based on the total amount of catalyst. The hydrocarbonaceous feedstock was passed upward. The catalyst volume density was 0.54. This method is 2
temperature of 15 °C, pressure of 32 bar and 1 (kg/kg
, hr ) (weight feedstock/weight catalyst) (7) WH
It was held at 3V. After 170 hours of operation, it was observed that 71% wt of the butenes present in the feed had been converted to normally liquid hydrocarbons. Comparative Experiment■ Substantially the same method as described in Example I was carried out at 300°C.
Comparative experiments were carried out at a temperature of 35 bar and a pressure of 35 bar. After 170 hours of operation, it was observed that 30% wt of the butenes present in the feedstock had been converted to normally liquid hydrocarbons. [0011] Example II A hydrocarbonaceous feed comprising 50% wt butene and 50% wt butane was passed upward through a reactor containing a catalyst containing mordenite in the hydrogen form. The catalyst volume density was 0.54. This method requires a temperature of 215°C, a pressure of 31 bar and 2. 5 (kg/kg, hr
) (Weight Feed/Weight Catalyst) (7) Performed in WH3V. After 260 hours of operation, it was observed that 45% wt of the butenes present in the feedstock had been converted to normally liquid hydrocarbons. [0012] Example III The amount of nickel present in the nickel containing nickel on hydrogen form mordenite is 10.0% based on the amount of mordenite.
3% wt nickel) and 2 based on the total amount of catalyst.
A hydrocarbonaceous feed comprising 50% wt butene and 50%-vt butane was passed upwardly through a reactor containing a catalyst that also contained 0% wt alumina. The catalyst was present as a fixed bed during the run. This method is
temperature of 215 °C, pressure of 30 bar and 1 (kg/k
g, hr) (weight feedstock/weight catalyst) WH3
It was held at V. After 210 hours of operation, it was observed that 76% wt of the butenes present in the feedstock had been converted to normally liquid hydrocarbons. Comparative Experiment III A comparative experiment was conducted by conducting substantially the same method as described in Example III, except that the kami feedstock was passed downward through the reactor. After 210 hours of operation, it was observed that 30% wt of the butenes present in the feedstock had been converted to normally liquid hydrocarbons. [0013] Example ■■ Catalyst containing nickel on mordenite in hydrogen form (the amount of nickel present is 1 based on the amount of mordenite)
0% wt nickel) to a reactor containing 50% wt nickel)
A hydrocarbonaceous feedstock comprising 50% wt butene and 50% wt butane was passed upward. The catalyst was present as a fixed bed during the run. The process was carried out at a temperature of 215[deg.]C, a pressure of 30 bar and a WH8v of 1 (kg/kg, hr) (weight feed/weight catalyst). Operation 1
After 60 hours, 75% wt of butenes present in the feedstock
was observed to be converted into liquid hydrocarbons under normal conditions.

Claims (9)

[Claims] 1. A process for producing normally liquid hydrocarbons from a hydrocarbonaceous feedstock comprising an olefin containing from 2 to 6 carbon atoms, comprising: residence in a reactor for at least 1 hour under reaction conditions; A process as described above, characterized in that the feedstock is passed upwardly through a reactor containing catalyst particles comprising a crystalline support at a temperature of from 150 to 295[deg.] C. and at elevated pressure. 2. A process according to claim 1, which is carried out at a temperature of 180 to 280°C. 3. The method according to claim 1, wherein the catalyst contains a crystalline aluminosilicate. 4. The method of claim 3, wherein the crystalline aluminosilicate is ZSM-5. 5. The method of claim 3, wherein the crystalline aluminosilicate is mordenite. Claim 6: Claims 1 to 5, wherein the catalyst contains nickel.
The method described in any one of the following. 7. A method according to claim 1, wherein the crystalline aluminosilicate is in hydrogen form. 8. The method according to claim 1, wherein the catalyst volume density is from 0.50 to 0.65. 9. Separating the resulting effluent into at least two fractions, wherein at least one fraction has a boiling range higher than the boiling range of the olefins present in the feed; 9. A method according to any one of claims 1 to 8, wherein at least a portion of the amount is recycled to the method.