DE1960487C - Process for the hydrogenation of heavy hydrocarbon oil - Google Patents

Description

seem to be literal in the part of the original

55 materials are concentrated in tetrahydrofuran

(THF) is insoluble. This material, also known

. · _D,. . . . ^as tetramethylene oxide, is a well known chemical

The invention relates to the hydrogenation of heavy solvents, but this is not normally the case with hydrogen, at least some of which are used in refining hydrocarbon oils, boiling at around 525 ° C. and substantial amounts of in 60%. Even that from a processing standpoint ■ contains anydrofuran (THF) insoluble material. Ability in the above-described type of hydrogenation of such oils can primarily be due to the production process, from the point of view of the most difficult heavy coal, heavy oil for the formation of low-boiling hydrogen raw material contains only relatively little than or to a desulphurisation of the oil or substantial amounts of material which is insoluble in THF be aligned with these reactions. 63, it is assumed that this material mostly ere reactions generally ζ in connection with material having a relatively high molecular weight Β; run n reactions, can of course also is over 500 000 ^barks in the conventional USAGE · dung purposes of the end products of the hydrogenation of sulfur

rer hydrocarbon oils nowhere real useful feedstock of less than 1 percent by weight brings the realization that the distance from in TH F decrease. In a preferred embodiment of the Invention of heavy hydrocarbon insoluble material contains the heavy hydrocarbon oil feedstock the machinability should be at least about 1.5 weight percent The starting material used in hydrogenation processes is "THF-insoluble material" and the treated Can improve significantly, allows improvements in the starting oil contains no more than about 0.5 Ge machinability without the disadvantage of the removal percent of material insoluble in THF, tion of large amounts of feedstock, such as heavy hydrocarbon feedstocks of which

would be the case when deasphalting with propane. a considerable part, usually at least some

According to the invention, considerable amounts of approximately 10 percent by volume are boiled at over about 525 ° C Heavy coal containing THF insoluble material and the considerable amounts of THF insoluble material Hydrogen source oil with THF to precipitate material, usually greater than 1 percent by weight of the THF-insoluble material in contact and often more than 1.5 percent by weight, brings. Material that is insoluble in THF is separated off are suitable starting oils for practical and the starting oil then in a conventional manner according to the invention. Usually special hydrogenated. difficult oils are those that are between about 1.5

The invention thus relates to a process and 5 percent by weight of material which is insoluble in THF and contains hydrogenation of heavy hydrocarbon oil. Starting materials of this type are at least 10 percent by volume above about 525 ° C comfortable residual oils, in some cases also oils that naturally occur in boiling constituents as well as tar sands insoluble in tetrahydrofuran, and other similar constituents. The process is thereby called sediment materials. For example, Vage indicates that a) at least some of these vacuum or atmospheric residual oils are suitable, as are also going oil with tetrahydrofuran as solvent in thermally cracked residual oil.

Is contacted in tetrahydrofuran insoluble There, all or a portion of the selectively precipitated to hydrierenliches material and separated »5 the heavy hydrocarbon starting oil with and b), the starting oil fraction with reduced amounts in IHL insolubles in accordance in tetrahydrofuran insoluble material in a with the invention are treated with THF, and there is a hydrogenation reaction zone for hydrogenation with a, it should be mentioned that the term "hydrocarbon hydrogenation catalyst and hydrogen-containing gas starting oil" includes both fresh material and re-hydrogenation conditions (temperature between 30 With hydrogenation process 370 and 480 ⁰ C, hydrogen partial pressure between ren, at which the reinstallation of heavy ends 70 and 210 atm, hydrogen supply between 0.2 and practiced wild, it may be desirable to use the ge-2 Nm ³ per liter of starting oil, space flow rate - all fresh material or it is brought into contact with some of this at a rate of between 0.2 and 5.0 vol./vol./h.) away from THF-insoluble constituents and, if necessary, treat the product, but it can also be desirable to use the product from the hydrogenation reaction zone is fractionated total recycled residual oil stream or a fraction with a high boiling point, in which part of it is additionally or as an alternative to treating at least 10 percent by volume of oil constituents over approximately the fresh material to be treated with THF. In any event, it is generally desirable that the removal of tetrahydrofuran-insoluble material be treated in the entire material and then be treated as at least one feed material for the hydrogenation reaction. Part of the heavy hydrocarbon feedstock is recycled to the both fresh material and hydrogenation reaction zones. recycled streams 1 weight percent des

The drawing represents a somewhat schematic explanation- all material should not exceed Modification of a Preferred Embodiment of FIG. 45 The invention is in a variety of hydraulic inventions method useful, but especially where it is

In conventional deasphalting with propane, heavy hydrocarbon feedstock oil would use the above heavy oil fraction to be deasphalted under the prescribed type for the conversion of at least about Turning propane into an asphalt fraction and a material boiling at 40% by volume at over 525 ° C deasphalted gas oil separated. The ratio of 50 in material boiling below about 525 C. separate components is around 40 to 50 will. Especially with this relatively high conversion weight percent Asphalt with about 60 to 40 passes used to be the most difficult weight percent deasphalted gas oil. in contrast with certain starting oils, which, as now in addition, the proportions of the paint found insoluble in THF are relatively large amounts of unrials in THF Contains soluble material in heavy hydrocarbon base oils.

rarely, if ever, greater than about 5 weight- The precipitation and removal of an in THF un-

percent, so that the starting oil removed by removing the THF-soluble material from heavy hydrocarbon-insoluble fractions from the starting oil can according to the invention be applied to any suitable Material very rarely 5 percent by weight of the original type are carried out using all exposure Starting oil exceeds. 60 knew techniques for liquid contact processes.

It has been found that the hydrogenation process can, for example, be carried out by conventional apparatus heavier hydrocarbon feedstocks with more than are used for countercurrent extraction, or 1.0 percent by weight of material insoluble in THF, the THF can simply be mixed up with the problem to be treated will. It is to be mixed in accordance with the raw material, the solids being .Invention therefore advantageous, starting material with 65 removed from a settling drum as a slurry more than one percent by weight of being insoluble in THF. One for conventional deasphalting primers To treat material with THF, to the corridors suitable device can z. B. for this total amount of the material insoluble in THF in the out-purpose use u, ^ »»

5 6

Since the THF-insoluble material, the invention per liter of starting oil are normal for such processes,

is removed according to, for the hydrogenation process also space velocities between about

is disadvantageous and with other refining operations 0.2 and 5.0 volumes of starting material per hour per hour

is not considered useful this volume of reactor capacity (V / hr / V) is gained.

Material generally preferably for recycling, 5 For use in the hydrogenation of inven-

for example as fuel. Because of the relatively at least partially treated carbon

At the high price of THF, the THI- 'vor- lenhydrogen starting oil can be obtained any natural or

preferably be suitable from the material insoluble in THF before synthetic hydrogenation catalyst, where-

the recovery of the insoluble substances. This applies to the composition, particle size and quantity

can be done by dissolving the insoluble in THF of such a catalyst is not part of the invention

borrowed substances in a suitable solvent such as are. Suitable catalysts are, for. B. cobalt,

o-dichlorobenzene or iron, molybdenum, nickel, tungsten and cobalt can be

happen, for example, by filtering the molybdal, like its oxides and sulphides on their own

elutriation of the insoluble substances from the THF or together with other suitable catalysts

Treatment stage, the liquid containing the carbon like naturally occurring silicates on suitable

hydrogen output stream is fed back and basics, such as alumina or silica-alumina,

the solids are discarded. If desired, the catalyst can be in a suitable form, e.g. B. as

Residues obtained from this feed can be solid bed, slurry or like that in the upper one

With a suitable material such as circulating oil for the aforementioned US Pat. No. RE 25,770

Convenient transportation are slurried. The 20 fluidized bed will be applied and will be pre-

Material insoluble in THI- 'can be discarded as waste, preferably in the reaction zone in the form of a mass

or conveniently burned as fuel. individual fixed parts be present, usually with a

Because of the aforementioned high price of THF at a concentration of at least about 317 kg per

the THF solution and that from the THF extrak- cubic meter reaction zone, with the mass through

tion stage, the recovered hydrocarbon effluent is the upward flow of the gas and liquid

gang oil preferably for the recovery of gas through the reaction zone in random motion

THI treated before the starting oil is kept hydrated. A catalyst in such beds can

procedure is subjected. This can be easily done in the form of finely divided particles of only approximately

using a conventional peeling process through 40 microns or in the form of larger particles such as the

with the TH F recovered from the oil and used in the fluidized bed in the upper

is reinstated for the extraklion stage. The US patent mentioned in the fluid is present,

The term "hydrogenation catalyst" as used here

of the THF-insoluble material is used, refers to any catalyst

can, of course, be treated similarly to remove THF regardless of additional

split off from the hydrocarbon starting oil. On 35 cash functions, such as cracking the coal

In this way it is generally possible to use vcr- hydrogens. . 11th

Equally little preparation effort for the egg

THI solvent to work; n. Typically, as shown in the drawing, fresh s: hweres occurs

the need for fresh solvent under such as hydrocarbon feedstock oil in the device

I percent by weight, based on the hydrocarbon 40 through a pipe 11 and flows in

Starting oil, the valve 12 insoluble in THF for removal in an extraction unit 13. The through the

Materials treated are kept. Pipeline 11 imported raw material is Ma-

In the treatment of hydrocarbon oils for materials with low sulfur residue from the central

the removal of substances insoluble in THF will become continent at a rate of 66,600 kg

suitable amounts of THF, roughly between! - and 45 per hour, and the following properties

20 times as much THF as the starting oil to be treated shark:

used in the extraction stage. It goes without saying. , _o

of course, that the amount of THF used and cur Ί 1 « 7- u

the amount of fresh THF processing required ^ chwefe ... 1.36 percent by weight s, ch depending on the amounts of in THF un 50 Ramsbottom carbon 15.4 percent by weight

soluble material in the starting oil to be treated, in the r

of operating conditions etc. change. , "" ". ''

The THF Extraction Stage and the Hydrogenation Stage Insoluble in Fntane "

can under suitable operating conditions through- ^ lenal 16.8 percent by weight

be guided. The THI treatment can, for example, 55 ? TT _nni ^ ^pur . ,

can be carried out at atmospheric pressure ^Asc t ^e · _f ; JSJ weight percent

the, while temperatures between about 0.39 nitrogen Qewichtsprozent

35 and 66 ⁰ C are kept. If desired, Y ₁ ³¹ V ^ " ¹ *? Tet e per million

higher temperatures and higher pressure can be applied to nickel 31 parts per gallon, as long as THF in the extraction stage 60 initial boiling point up to

remains in a liquid state. The hydrogenation rate? Ϋ _k ö ^ '",'" ^ ^{oum percent}

The treated starting oil can be driven below 525 C 92.8 percent by volume

conventional increased temperature and pressure in iiif uniosucnes

conditions are carried out. The temperatures material 3.7 percent by weight

are normally between about 370 and 65. In the extraction chamber 13 this is determined by the

480X and the pressure approximately between 70 and 210 atmospheres. Pipeline U imported starting material iüii IHF

Hydrogen partial thick. Amounts of hydrogen brought into contact between that in the extraction unit

approximately 0.2 and 2 standard cubic meters of hydrogen is introduced through conduit 14. The

■ = * £ ■

'vr-rt

⁷ 8

»1, TH (--- solvent becomes approximately in the ratio IO From the separation zone 32 liquid becomes dual

^hr i "Iu TTTlI ^PrO Ausgan ^ smaterial vcr- a pipeline 34 withdrawn and a fraction *

turns. The extraction process is fed to a tempering system 35, where it is converted to a petroleum

temperature of 66 C and be, atmospheric pressure fraction, which by a pipe 3cnfnommcr

n- ■ carried out. Line slurry of starting oil, 5 being, a hydrogen oil fraction, which is produced by a RoTiHd-

THI- and precipitated, m THF-insoluble material tion 37 and a residual oil which is produced by dnc

is taken through a pipe 16 from the extraction pipe 38, fractionated w rd D

cmhc.l removed and removed to a filter device 17 through the pipeline 38 residue

broke, where solid material that is insoluble in THF is removed through a Rohrlc tu g ™ 3 and a Jen!

separates and is removed through a pipe 18. , "Til 44 and won as a process product

This material can be used as fuel, the entire residue factor can also be used

_; : Wöbe, man, hmm, a slurrying liquid through the part of the pipeline, a

TÄ " ^{JUf JCdC alUlere 8eeißnete} ? Ζ" ^{ei Vtn 41 fÜh}

WeTse WÄ ^{J alUler} ? Ζ "f! ⁿ ' ^{To ZUSät7lidl} CS

_n are as ncscitifct provide for the Hydr.erungsreaktor 26 or

The fluid 15 withdrawn from the extraction system 13 can be closed through the pipeline 38 and a valve 42

s.gkc.t nut the m THr insoluble material is forwarded from pipeline Π, from where it passes through the

the holding system 17 through emc pipeline 19 suitable extraction system 13 for removing η THF u, -

tcrwc.se nwme pipeline 21 returned, where soluble matter is passed before s ° c again / um

Me nj the mixture of purified starting oil and reactor 26 is passed. The return rate of

THF recovered from the extract

come, and is led to a Absimfanlage 22. approximately up to ten times the leadership rate "

In the stripping plant 22, the THF solvent is removed from the fresh material through the pipeline

separated from the starting and / ur extraction system 13 As indicated in the description above, in

returned through pipeline I Depending on the BE THF insoluble material either L to the frScS

Fresh Tllr reprocessing solution can be used * ₅ feed material or from a ruXcführ 12

be introduced through cmc pipeline 23. Residue fraction or both

Starting oil with reduced amounts of in THF If desired, either cm Te Trisches

Insoluble material is removed from the stripping system 22 material or return liquid for the removal in

treated by cmc pipeline 24 and a heater 25 for the THF insoluble stiff wc de, tr

Starting material for a hydrogenation reactor 26 30, corresponding setting of the valves T ₂ 28 41 to

guided. Emc secondary line 27 and a valve 28 to 42 to control the quantities of fresh supply andI through

Bypassing the fcxlrak ion system drove the entire return line routed to the extraction system 13

fresh starting material or cm part of it to be coordinated directly with it

to the hydrogenation reactor, if desired. ^{naturally differed} ™ ^ n = »^ ι ivi - '» ^j "™ m- sinu

Solid clay insoluble in THF as filter cake ₃₅ ^ tt Ϊη ^^^ ΓM ^ M ^ fr, ^

from the filter device 17 m a quantity of starting material and the material to be stirred back are andIiS

40 kg h removed and thus reduce the amount of to what extent such material is removed so Γ

I hl insoluble substances in the reactor 26 Generally speaking, ir 7> wX ^{weracn si11}

guided output ", to 0.5 percent by weight, fns level of JmSSung S ffi" "SigoTTesS

total w, rd starting oil with 64,500 kg dissolved in THF 40 lower the maximum permissible volume in THF

hchem Matenal stundl.ch through the pipeline 24 insoluble material in the AugnSa rml for the

_4n hydrogenation,
reactor 26 introduces through a pipe 29, fm

for the

USA patent by upstreaming instead of 'trying this'

Liquid and gas through the catalyst bed in distant when in the frkrhon

held in a whirled state. In this example, ^ "^ '" ^^ ° ^lc . ™ ^en S ^{e an is insoluble in THF}

the catalyst is a molding made of cobalt molybdenum 50 you return rate toS,? " ⁸ !" , ^{1Cdrig md}

on Alununium _ha t and a cut is high. l ^ n ^ iSn SM "Ϊ ^^ ΓΙηΪ

Diameter of 0.8 mm. The hydrogenation zone becomes insoluble material throughout the 7 »Khr .

at a hydrogen partial pressure of about 160 atmospheres for the reactor *. ,, »^ - feed material

a total pressure of 210 atmospheres, a liquid ^ ring. by ££ ^ _ΤΗ ΤΓη? ΪΞ _£ sf π ""

room velocity of 0.7 V / hour / V, a temperature described above from the backlnHc t 'J - ~ u, ^W ' ^C

temperature of 450 "C and removed with an addition of hydrogen. Such a Si ^ J ^ f, ü ^m

0.735 normal cubic meters per liter at the reacfor inlet has the weK% Sf * 2 i2f? "THF ? '\ ° T

held. The catalyst addition is 0 28 e Kata- material das Luι J · ^J , ^{HF insoluble}

lysator per liter of starting material enS becomes Z, "^ -" iT « ⁸ ^ ¹⁰ '8 ^{e is formed} -

From d ^P em reactor 26 the product through a 60 ÄÄSÄ Entferf £ ^ "^ ~""is

Pipeline 30 withdrawn, handled by a pressure-reduction insoluble material ^ "S"" ^{8 V} °"'"zjerventil 31 led to a separation zone 32, in

which separates the liquid from the vapor. The example 2

Steam from the separation zone 32 has a high under-condition

Hydrogen content and becomes large in the reactor by the 65 of the distance

Pipeline 29 is fed back. Hydrogen to the material from the

The whole is hydrogenation reactor 1 through a pipeline 33 as required

^ADDED - ⁶² "o of ^the W over about 525 C boiling starting

materials in material boiling below about 525'C be operated, for this example 2 the procedure carried out the same as described above, except that no Till-insoluble materials voip Starting material can be removed. With these conditions clogs the 1 hydration rcaktoi '26 with coke

10

and polymeric material, and the process will considered impracticable. With no removal of THF insoluble material, reactor 26 is only to a maximum degree of conversion of 30%, a temperature of 438 ° C and a room temperature digkcit of 1.0 V / hour / V can be activated.

1 sheet of drawings

Claims (4)

1 2 The techniques for carrying out the hydrogenation patent claims: Such a starting material at a large number of operating conditions are well known and one 1. Process for the hydrogenation of heavy carried out. In some of the known processes for hy-hydrocarbon oil, the at least 10 volume production of heavy hydrocarbon oils is the carbon components boiling above about 525 ° C as well as hydrogen oil together with hydrocarbon haline Tetrahydrofuran-insoluble components degas gas in an intimate vapor-liquid mixture holds, characterized in that an amount of a solid hydrogenation a) at least part of this starting oil with catalyst-containing reaction zone with a Ge-tetrahydrofuran as solvent in contact io speed which is sufficient to keep the solids in random motion insoluble in tetrahydrofuran, and under such conditions material is selectively precipitated and separated after directed above that there is a net chemical consumption and _{there is} hydrogen and the hydrocarbons in b) the starting oil fraction with a reduced amount of material flowing out of the reaction zone The substances insoluble in tetrahydrofuran are at least partly in the liquid phase. One for A catalyst system suitable for such processes in a hydrogenation reaction zone Hydrogenation with a hydrogenation catalyst is e.g. B. the well-known fluidized bed system (USA.-Patent and hydrogen-containing gas under hydration RE 25 770). conditions (temperature between 370 in the hydrogenation of heavy hydrocarbon oils and 480 ⁰ C, hydrogen partial pressure between ao one sometimes encountered considerable difficulties 70 and 210 atu, hydrogen supply between 0.2 and 2 Nm ³ per liter of starting oil due to clogging and deactivation, space catalysts due to constituents in the starting material, flow rate between 0, 2 and and by polymeric material believed to be 5.0 v / v / hour) that it is formed by these components. The suggestion has previously been made, and possibly the product of the Hy- 25, that the initial hydration reaction zone is fractionated and material is subjected to conventional deasphalting with a fraction with a high boiling point in which propane, such as is used, for example, in US Pat. B. in the Belgian at least 10 percent by volume oil components patent 615 469 is described to remove the heavy boiling above about 525 ° C, with tetrahydrofuran components from the material. It was believed that the portion of the starting material treated with hydrofuran-insoluble materials for the hydrogenation of such starting material and then creates as at least part of the heavy hydrocarbon starting oil contained in the heavier constituents is believed to be solvents for removing solvents in Tetra-30, which are so removed so that the deasphalted hydrogenation reaction zone recycled material can then be processed easily in conventional hydrogenation equipment approximately ™ ^ird · 35th For implementation 2. The method according to claim 1, by identifying this method, the proposal was made, notes that a heavy hydrocarbon residue was removed by deasphalting with propane oil with originally more than 1 weight pro-heavier materials later in the product from the cent of tetrahydrofuran-insoluble material hydrogenation treatment could be back-mixed, is used and the content of this material 40 The amounts of by deasphalting with propane before hydrogenation to less than 1 percent by weight or even using slightly heavier cohesion, preferably less than 0.5 percent by weight of hydrogen solvent removed, is decreased. material are unfortunately so large that a backmixing 3. The method according to claim 2, characterized in that all of the material is included in the product ^; In many cases it is noted that the content of oil in tetrahydrofuran makes it impossible to reduce products with sufficient low-chemical material to such an extent that the lower sulfur content can be produced and, if the starting oil fraction is essentially free from, can be mixed back into heavier parts tetrahydrofuran is insoluble material. In addition, some of the metals or other constituents 4. The method according to any one of claims 1 to 3, these heavier proportions problems with the further processing marked that only the recirculated 50 cause the oil to work. Proportion of the starting oil for the hydrogenation reac- It has now been found that the constituents are tion zone with tetrahydrofuran solvent of certain heavy hydrocarbon starting oils, which is traded. _for p _ro problems responsible for the hydrogenation of such oils