JPS61143490A - Hydrogenation conversion method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improvements in slurry hydroconversion processes using gold-containing catalysts made from catalyst precursors dispersed in hydrocarbons.

Slurry hydroconversion processes using catalysts made in hydrocarbon oil from thermally decomposable or oil-soluble metal compound catalyst precursors are known. For example, US Pat. No. 4.22474
See No. 2 and No. 4.244.859.

It is also known to use such catalysts in hydroconversion processes (ie, coal liquefaction) in which coal particles are slurried in a hydrocarbonaceous material. See, eg, U.S. Pat. No. 4,077,867 and U.S. Pat. No. 4,111,787.

The term "hydroconversion" in connection with hydrocarbonaceous oils is used herein to refer to the conversion of at least a portion of the heavy components of the oil to lower boiling hydrocarbon products carried out in the presence of hydrogen. Used to refer to a catalytic process that simultaneously reduces the concentration of nitrogen-containing compounds, sulfur compounds, and metal components.

All boiling points referred to herein are boiling points equivalent to atmospheric pressure unless otherwise specified.

Now, after the catalyst precursor mixed in a relatively large amount in the hydrocarbon oil (i.e., catalyst precursor concentrate) is pretreated to convert the catalyst precursor into a solid catalyst in the oil, the generated catalyst concentrate A part of the water is hydroconverted (hydrocon
vert@d) Introducing treat gas (H2S and It has been found that the use of H2) provides several advantages, such as greater flexibility in heat balance and greater energy economy. Also,
By treating only the catalyst precursor concentrate, less equipment is required than when treating the entire feedstock. Moreover, by making the catalyst concentrate) it is possible to store the catalyst concentrate and use it when needed on site or send it to another location.

According to the invention, (a) a heavy hydrocarbon oil and about (L2 to about 2.00 weight f) on a weight basis of the hydrocarbon oil calculated as metal elements;
of the oil-dispersible metal compound in an amount ranging from 1.0% to 5.0%, the metal being a compound of an oil-dispersible metal in the periodic table of elements IV, V, V.
(b) combining the mixture resulting from step (a) with the presence of a gas selected from the group consisting of a hydrogen-containing gas, a hydrogen sulfide-containing gas and mixtures thereof; (c) heating the oil-dispersible metal compound in the hydrocarbon oil under conditions that convert the oil-dispersible metal compound into the corresponding metal-containing solid catalyst in the hydrocarbon oil; (d) hydrogenating the resulting slurry containing the hydrocarbonaceous charge and the solid catalyst by subjecting it to hydroconversion conditions in the presence of a hydrogen-containing gas; A slurry hydroconversion process is provided that includes producing a converted normally liquid hydrocarbon product.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring to the drawings, a heavy hydrocarbon oil is introduced into the mixing zone 1 by line 10 . A heavy hydrocarbon oil suitable for introduction into mixing zone 1, which may also serve as a catalyst preparation zone, contains components with boiling points above 1050°F (566°C), preferably with a reduced content of components with boiling points above 10507°C. Tomo 10-fold N
% hydrocarbonaceous oil, such as crude oil, with a boiling point of 650°F
Atmospheric distillation residual oil with a boiling point of 10507 (343℃)
Contains vacuum distillation residues exceeding . Preferably, the hydrocarbon 'iitm has an initial boiling point higher than at least 6507 and contains asqualtene. As an alternative to using one zone, such as mixing zone 1, as both a mixing and catalyst preparation zone, a separation zone or vessel can be used after mixing zone 1 to prepare the catalyst (i.e., the catalyst precursor into a solid catalyst). Most preferably, the hydrocarbonaceous oil contains at least 2
Species hydrocarbonaceous oils, i.e. boiling points of about 975'F (5
24° C.) A blend of a light boiling fish oil with a lower boiling point than 9757 and a heavy oil with a boiling point higher than 9757, containing at least 10 parts by weight of material with a boiling point above 10507, preferably about 25 parts by weight.
%. The preferred concentration of heavy oil in the blend is between 25% and 25% based on the weight of the blend (mixture of oils).
90[(31% M quality oil, preferably 45-90% by weight)
of heavy oil, most preferably 45 to 75 salt fit% by weight
Including 1 night. Light oils can be gas oils and heavy oils can be vacuum distillation residues. Instead, add atmospheric distillation residual oil containing an appropriate amount of desired components to pipe 1o.
It can be used as an oil. The hydrocarbonaceous oil carried in line 1o may be obtained from any source such as petroleum, tar sands oil, silica, liquids derived from coalification processes, and any mixtures of these oils.

These oils weigh about 5 to 50! It is common to have a Conla Vson carbon content in the range of #% (see A8TM test D189-65 for Conla Vson carbon content)
. An oil dispersible metal compound (catalyst precursor) is introduced into the mixing zone 1 via line 12 . The oil-dispersible metal compound is a compound that is soluble in hydrocarbon oil, or a compound that is soluble in an organic compound (liquid medium fK) that can be dispersed in hydrocarbon oil, or a water-soluble compound that can be dispersed in a water bath. The liquid may be capable of being dispersed in a hydrocarbonaceous material. The oil-dispersible metal compound introduced through conduit 12 is a phenolic medium,
Can be added to water, alcohol, etc. Suitable oil-dispersible metal compounds that can be converted (under the preparation conditions) into solid metal-containing catalysts include (1) inorganic metal compounds, such as carbonyl, pallite, oxybarite V: polyacids, such as isopolyacids, heteropolyacids (e.g. (2) Organic acids, such as acyclic and cycloaliphatic carboxylic acids and thiocarboxylic acids containing 2 or more carbon atoms (e.g. naphthenic acid): Aromatic carbon M (e.g., tb,)ruyl #): sulfone m< e.g.
Toluenesulfonic acid); Sulfinic acid; Mercaptan:
Xanthogen W1: metal salts of phenol, di- and polyhydroxyaromatic compounds, (3) metal salts with organometallic compounds such as 13-diketone, ethylenediamine, ethylenediaminetetraacetic acid, phthalocyanine, etc.),
(4) Organic amines, including aliphatic amines, aromatic amines, and metal salts of quaternary ammonium compounds.

The metal component of the oil-dispersible metal compound that can be converted into a solid metal-containing catalyst is found in elements 11, I, IVSVSv of the Periodic Table of the Elements.
a group consisting of IBS B and Vl groups and mixtures thereof;
Precious metals including zinc, antimony, bismuth, titanium, cerium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, fupartite, nickel and platinum, iridium, palladium, osmium, ruthenium and rhodium. Preferred metal components of the selected dispersible metal compound are selected from the group consisting of molybdenum, tungsten, vanadium, chromium, cobalt, titanium, ferrous nickel, and mixtures thereof. Preferred compounds of the given metal include salts of acyclic (straight or branched chain) aliphatic carboxylic acids, salts of cycloaliphatic carboxylic acids, polysaccharides, carbonyls, phenolates, organoamine salts. .

The periodic table of elements referred to in this specification is referred to in "Hendrupku Opunamistrian V Physics J19+" published by O^io, Creepland, Chemical Rubber Publishing Co., Ltd.
Published in the 45th edition in 1964. Such oil-dispersible metal compounds are described in US Pat. No. 4,295,995. Preferred oil-dispersing compounds are inorganic polyacids of metals selected from Groups VB and VIB and mixtures thereof, namely vanadium, niobium, chromium, molybdenum, tungsten and mixtures thereof. Suitable inorganic polyacids include phosphomolybdic acid, phosphotungstic acid, phosphovanadic acid, silicoolibdic acid, (slllcoolybdlc ac
ld) including silicotungstic acid, silifvanadic acid and mixtures thereof. A preferred polyacid is phosphomolybdic acid. The terms "heteropolyacid" and "isopolyacid" are used herein as
Publisheders, “Adv@H(@dInorganic c
hamlstrF) J, 3rd edition, 950-95D with Nis nee Cotton (S, person * Cotton) and Ji x
7 Geoffrvy Wilkinson
used according to the definitions listed by Aon).

Gas is introduced into the mixing zone 1 via line 14. The gas is selected from the group consisting of hydrogen-containing gases, hydrogen sulfide-containing gases, and mixtures thereof. The gas is hydrogen and about 1
and about 90 mole percent hydrogen sulfide. Add a sufficient amount of oil-dispersible metal compound (catalyst precursor) to mixing zone 1.
introduced into the catalyst precursor concentrate, i.e. calculated as a metallic element based on the weight of the hydrocarbonaceous oil in the mixture (
Form a mixture containing L2 to 2% by weight, preferably (L2 to 1% by weight, more preferably about 13 to 1% by weight) of metal.A mixture of an oil-dispersible metal compound and a hydrocarbonaceous oil. (
Catalyst precursor concentrate (concentrate) is mixed in zone 1.
, or in any subsequent zone that may be used as a catalyst preparation zone, to a temperature sufficient to convert the oil-dispersible metal compound (catalyst precursor) to the corresponding metal-containing solid catalyst. Suitable tactile mmg conditions are approximately 500' to 779°F (
260° to 415°C), preferably 65oo to 779°
F (343° to 415°C), preferably about 680°
Temperatures ranging from ~750°F (360° to 388°C) and 50 to 5000 palg (xs ~350KP/
cI41G), preferably 100-20
The oil-dispersible metal compound is converted to a solid catalyst containing a metal corresponding to that of the catalyst precursor using a pressure in the range of OOpalg (7-140 Kp/c in G). The resulting catalyst concentrate (solid catalyst particles dispersed in hydrocarbon oil) is removed from mixing zone 1 through line 16. At least a portion of the catalyst concentrate is introduced into line 18 carrying a 5 It hydrocarbon charge. The catalyst concentrate is dispersed in the oil charge. A suitable hydrocarbonaceous charge is crude oil, with a boiling point of 430°F (221°F).
℃), preferably less than 650°F (343°C).
gh) :! -1y-tower m fFh .

The hydrocarbonaceous oil may be derived from any source, such as petroleum, rock oil, tar sands oil, oil derived from coal liquefaction oil containing coal liquefaction bottoms, and mixtures thereof. It is preferred that the hydrocarbon oil has at least 10% by weight of materials with boiling points above 1050°F (564°C). Hydrocarbons range from about 5% to about 50%.
It is more preferred to have a Vson carbon content.

Hydrogen-containing gas is introduced into the pipe line 2o and into the multi-pipe line 18. A mixture of hydrocarbonaceous charge, catalyst concentrate, and hydrogen is passed through line 18 to the slurry-hydroconversion chamber 2. Conduit 1
6 catalyst concentrate as a hydrocarbonaceous charge, based on the entire hydroconversion area feedstock, that is, the concentrate + hydrocarbonaceous charge, and calculated as a metal element from about 10 to about 2000 W.
i)l)m metal, preferably from about 50 to about ICl
Add in an amount to give 0.00 wppm of metal.

Appropriate slurry hydroconversion operating conditions are summarized in Table 1.

Table 1 Humidity, °F (c) aoo~900 (427-4
82) Take out the 820-870 (438-466) hydroconversion zone effluent through the pipe 24 and transfer it to the gas-liquid separation zone 5
, where the normally gaseous phase and the normally liquid phase are separated. The gas phase is removed from the separation zone 3 via line 26. Alternatively, the hydrogen-containing gas phase can be recycled to the slurry hydroconversion zone 2 via line 20 (via line 28), preferably after removal of undesirable components. The normally liquid phase containing catalytic solids in the hydroconverted hydrocarbon oil product is passed through line 30 to separation zone 4 and separated by conventional means such as distillation to separate light, intermediate boiling, and heavy It is converted into a quality column bottom oil fraction. The light fraction is removed through a pipe 32. The middle distillate is removed via line 34). A heavy bottom oil fraction can be removed in small quantities via line 36 and, if desired, at least a portion of the bottom oil fraction can be recycled to the hydroconversion chamber 2.

The following examples are presented to illustrate the invention.

``1 encounter 1B1!
ave Engine@ers) Cold Lake crude oil (cold Lak@Cru) was placed in a magnetically stirred autoclave.
de) 300JI underwater Crob (F) 2.5 j
i jt % (7) Charged with solution 46161.

The autoclave was flushed with nitrogen and heated to 121° C. with stirring and nitrogen flow at 3 liters/min. 1
After reaching 21°C, nitrogen stripping was continued for 30 minutes to remove all water. The autoclave was cooled and discharged to produce a catalyst front concentrate containing 2000 wppm Cr.

The catalyst precursor concentrate was treated according to the procedure of Preparation A and, after cooling, the concentrate was subjected to the following treatments.

The autoclave was incubated at room temperature with H2 for 7 lapses, then with H2S at 125 psig (a8Kp/CI+"G
) and then 1250 plg (s z
The autoclave was then heated to 580°C with stirring and heated to 380°-385°C.
for 30 minutes, then cool, depressurize and drain for 20 minutes.
Activated catalyst IIJ & concentrate containing 0.00 wppm Cr was produced.

Heavy Arabian (HaaVFArabia
n) 20% solution of phosphomolybdic acid in atmospheric residual oil 3921 and phenol a, o o
g was charged. H the autoclave! flash with
Then 125 paIg (8,8KP/cx
”G) and hydrogen for 12 s Opsig (879K
F/αme). The autoclave was then heated to 380°C with stirring and kept at 380°-385°C for 50 minutes before being cooled and evacuated to 2000 W.
lll] Pm containing Mo 2 active catalyst tIJks thick material was produced.

Example 1 (Experiment 1079) Heavy 7 Labian Vacuum Residual Oil 910I in a 5 oocc Autoclave Engineers Magnetic Stir Autoclave
i, heavy Arabian atmospheric distillation residue 1zoII, and catalyst concentrate 1'-BJ15. OJI was charged. The chromium concentration in this mixture was 250 Wppm. The autoclave was latched with H2 at room temperature for 7 hours, and H,f
9 to 1009mlg (7KP/11”G), and then hydrogen to 1550pmlg (109Kp/
cm"G).

The autoclave was then heated to 830°F (4
45°C), where the pressure was increased to 2200 pstg (
155,114/cm"G) and maintained these conditions for 3 hours. During that time, hydrogen was flowed into the autoclave, and the output gas flow was measured at room temperature with a wet test meter to a rate of 24 liters/min. The autoclave was cooled and depressurized. The gas was collected and analyzed by mass spectrometry to determine gas formation. The contents of the autoclave were collected in toluene solution and filtered to determine the solid content. was isolated, the solid was washed with toluene and dried at 100° C. for 1 hour in an open vacuum.

A solution of the liquid product in toluene was distilled using a 15/1 distillation to remove solvent and light liquids, followed by an a-C distillation to isolate the unconverted 975+°F (524+"C) material. Analyze the Conradson carbon of the 975+7 substance and determine the Conradson carbon conversion rate.

By these means, the toluene-insoluble coke yield based on the 975+7 content of the charging material was determined.2.
78 weight it%, 9.975+7 conversion rate is 87.4%
Adashi, CI-Cs gas yield based on all raw materials is 477%
Conradson carbon conversion to oil + gas is 58.
It was 9%.

Comparative Example I (Experiment 10661 066) I! The experiment was carried out according to the procedure of Example 1 except that rAJ catalyst precursor concentrate was used.

The toluene-insoluble coke yield based on the 975+7 content of the charging material was 3.61%, the 975+T conversion was 8 & 9%, and the C1-aS gas yield based on the total feedstock was 7.63. %), and the conversion of Con2dson envy to oil+gas was 519%.

Example 2 (Run 927) The experiment was conducted according to the procedure of Example 1 except that an active catalyst concentrate of prepared rCJ was used.

The toluene-insoluble coke yield based on the 975+7 content of the charge is 2.35% by weight, the 975+7 conversion is 8&2%, and the Ct-Cs gas production is 7.11% based on the total feedstock. %, the conversion rate of Conradson carbon to oil and gas was 56%.

The results of these experiments are shown in Table 1.

■ Rate 87.4 85.
9 85.2 Based on all raw materials (c@-Cs gas, wt% 477 Z63
7. Conversion rate to 17s, % 5B, 9
519 56.0 Preparation of catalyst precursor concentrate D
(Run 424L) The catalyst precursor concentrate was cleaved according to the procedure for Preparation rAJ, except that Cold Lake crude oil or Heavy Arabian Atmospheric Residue was used as the hydrocarbon medium.

Preparation of Catalyst Concentrate g (Experiment 426L) A concentrate of catalyst precursor was prepared according to the preparation procedure and after cooling the concentrate was subjected to the following treatments.

The autoclave was laundered at room temperature for 7 hours, then 1s o pstg (11Kp/ca”a) at Hx8.
) and then 1400 pmlg (98
KF Car G) was pressurized. The autoclave was then heated to 380°C with stirring and held at 380°-385°C for 30 minutes, then cooled, depressurized and evacuated for 20 minutes.
This resulted in an active catalyst concentrate containing 0.00 wppm Cr.

A 300 cc Autoclave Engineers magnetically stirred autoclave was charged with Topl Cold Lake crude oil 105.011 and catalyst precursor DJ15.OII (chromium concentration in this mixture was 250 Wpl). The autoclave was washed 7 times at room temperature, and the temperature was 50 pm with H219.
Pressurize to 1g (55 Kp/m"G) and then 1400 pmig (98Kp/cI4"G) with hydrogen.
Pressure was applied.

Claims (1)

[Claims] 1. (a) a heavy hydrocarbon oil and an amount in the range of about 0.2 to about 2.00% by weight calculated as metal elements based on the weight of the hydrocarbon oil; forming a mixture with an oil-dispersible metal compound, said metal being a member of elements II, III, IV, V, VIB of the Periodic Table of the Elements;
, VIIB, VIII and mixtures thereof; (b) the mixture resulting from step (a) is treated with a hydrogen-containing gas;
(c) step ( (d) introducing at least a portion of the hydrocarbonaceous oil containing the catalyst resulting from b) into a hydrocarbonaceous charge; and (d) forming a produced slurry containing the hydrocarbonaceous charge and the solid catalyst. 1. A slurry hydroconversion process comprising the step of subjecting the slurry to hydroconversion conditions in the presence of a hydrogen-containing gas to produce a hydroconverted normally liquid hydrocarbon product. 2. The heavy hydrocarbon oil in step (a) is at 1050°F.
2. A method according to claim 1, comprising a substance with a boiling point higher than (566° C.). 3. The method of claim 1, wherein the heavy hydrocarbon oil of step (a) comprises a blend of gas oil and vacuum distillation residue. 4. The method according to claim 1, wherein the heavy hydrocarbon oil in step (a) is an atmospheric distillation residue. 5. The oil-dispersible metal compound is added to the heavy oil in step (a) and the metal element is calculated as about 0 on the basis of the heavy oil.
．． 2. The method of claim 1, wherein the mixture is in an amount ranging from 2 to about 1.00% by weight. 6. The method according to claim 1, wherein the oil-dispersible metal compound is selected from the group consisting of inorganic metal compounds, salts of organic acids, organic metal compounds, salts of organic amines, and mixtures thereof. 7. The method according to claim 1, wherein the oil-dispersible metal compound is phosphomolybdic acid. 8. The metal of the oil-dispersible metal compound is molybdenum,
2. A method according to claim 1, in which chromium, vanadium and mixtures thereof are selected from the group consisting of chromium, vanadium and mixtures thereof. 9. The oil-dispersible compound is heated to a temperature of about 500° to 779°F.
(260° to 415°C) and total pressure about 50 to about 50
00psig (about 3.5 to about 350Kg/cm^2G)
and the hydroconversion conditions in step (d) are within a temperature range of about 800° to
about 900°F (about 427° to about 482°C) and hydrogen partial pressure range from about 100 to about 5000 psig (about 7 to about 350K)
2. The method according to claim 1, comprising: g/cm^2G). 10. In step (c), a portion of the hydrocarbonaceous oil containing the solid catalyst is added to the hydrocarbonaceous feedstock at a concentration of about 10 to about 2000 wppm calculated as metal elements based on the hydrocarbonaceous feedstock. 2. A method according to claim 1, wherein said metal is introduced in an amount such that said metal is