CN109897670A - A kind of hydrotreating method of heavy hydrocarbon feeds - Google Patents

Abstract

The invention discloses a kind of hydrotreating methods of heavy hydrocarbon feeds.This method comprises: up-flow reactor is connected at least one down-type fixed-bed reactor, heavy hydrocarbon feeds pass sequentially through up-flow reactor and down-type fixed-bed reactor, and down-type fixed-bed reactor effluent is isolated to each product；A kind of following hydrotreating catalyst is at least loaded in the up flow type hydrogenator；The hydrotreating catalyst includes carrier and active metal component, wherein the carrier is the spherical shape with two through channels, the overall diameter of ball is 5.0~8.0mm, and two passes pass through the centre of sphere and orthogonal through-hole, and channel diameter is the 30%~60% of ball overall diameter.The overall performance of catalyst can be improved in the method for the present invention, realizes that up flow type catalyst is synchronous with the catalytic performance of fixed bed catalyst, improves catalytic activity, extends operation cycle.

Description

A kind of hydrotreating method of heavy hydrocarbon feeds

Technical field

The present invention relates to a kind of hydrotreating methods of heavy hydrocarbon feeds, specifically, being to be related to a kind of including reduced crude With decompression residuum interior heavy hydrocarbon feeds hydroprocessing technique.

Background technique

It weighs, deteriorate as crude oil increasingly becomes, more and more heavy oil, residual oil need working process.The processing of heavy oil, residual oil Its cracking is not only low-boiling product, such as naphtha, intermediate oil and vacuum gas oil (VGO) by processing, but also to be mentioned High their hydrogen-carbon ratio, this just needs through decarburization or adds the method for hydrogen and realize.Decarbonization process therein includes coking, solvent Depitching, heavy oil catalytic cracking etc.；Hydrogenation technique include be hydrocracked, hydrofinishing, hydrotreating etc..Hydrogenation technique can add Hydrogen converts residual oil, improves the yield of liquid product, and can also remove hetero atom therein, good product quality, has apparent Advantage.But hydrogenation technique is catalysis processing technology, and there are hydrogenation catalyst deactivation probs, and especially processing is inferior, heavy hydrocarbon is former When material, Catalysts Deactivation Problems are more serious.For the cost for reducing heavy, poor residuum is processed, increase oil refining enterprise's profit, Currently, the technique of processing more heavy, poor residuum is still based on decarbonization process, but its poor product quality is post-processed It could utilize, wherein deasphalted oil and the especially needed carry out hydrotreating of wax tailings fraction, can just continue to use catalytic cracking Or be hydrocracked equal lightings device and processed, therefore, each oil refining enterprise separately have deasphalted oil and wax tailings plus Hydrogen processing unit.

Heavy oil, the slag oil cracking rate of residual hydrocracking technology are lower, and main purpose is for downstream raw material lighting device Such as catalytic cracking or coking device provide raw material.By hydrotreating, contain the sulphur in poor residuum, nitrogen, metal impurities Amount and carbon residue are substantially reduced, to obtain the acceptable charging of downstream raw material lighting device.

In fixed bed residual hydrocracking technology, according to the type of flow of the reaction stream in reactor, reactor class Type can be divided into common fixed bed reactors and flow downward mode reactor and up flow type (UFR) reactor.UFR reactor can To reduce the tenor in charging, effectively slow down the generation of bed pressure drop, therefore, UFR reactor is generally located on fixed bed Before reactor (downward stream mode), protection fixed bed reactor catalyst bed is because of bed pressure drop caused by operating later period metal deposit It increases rapidly and is forced to stop work.Up-flow reactor technology characteristics are that gas mixture is fed from reactor bottom upwardly through upper Streaming catalyst bed, and be that liquid phase is continuous in reactor, gas phase passes through in bubbling form, keeps entire catalyst bed light The deposits such as microdilatancy, metal and coke can be uniformly deposited on entire catalyst bed, avoid concentrating on a certain part, compared with The performance for having played all catalyst well slows down the rapid growth of catalyst bed pressure drop.It it requires that catalyst not only has There is higher hydrogenation activity, also wants crushing strength with higher and wear-resisting property.Because catalyst is at high temperature under high pressure anti- Catalyst in device is answered to be constantly in microdilatancy state, collision and rubbing machine can be more, are easily broken and wear, and increase catalyst and disappear It consumes or is adversely affected to downstream reactor and equipment belt.In addition, to the bulk density, grain shape, size distribution of catalyst Also there is certain requirement, it is generally recognized that the spherical shape more tiny for granularity than convenient grain shape.

In the group technology of existing UFR reactor and down-type fixed-bed reactor, UFR reactor catalyst is only capable of taking off Except part metals, and there is the extension with the duration of runs, the decline of UFR reactor catalyst demetalization performance obviously with flow down Formula fixed bed reactor catalyst performance and the cycle of operation mismatch.In view of up-flow reactor catalyst by removing metals ability has Limit needs to load a certain proportion of catalyst for demetalation in subsequent down-type fixed-bed reactor.But up flow type demetalization energy When power decline is obvious, the catalyst for demetalation of fixed bed reactors filling is difficult to undertake the load of decline again, leads to subsequent flow down Formula fixed bed reactors high activated catalyst affects the high activated catalyst of down-flow fixed bed by Metal toxicity, causes to urge Changing activity cannot give full play to, and be unfavorable for extending operation cycle.

Hydrodesulfurization and demetalization are two important reactions and heavy-oil hydrogenation in the heavy raw oils hydrogenation process such as residual oil The main target of modification.The difficult point of Residual cracking is asphalitine conversion.The chemical structure of asphalitine is extremely complex, is by polymerization virtue Hydrocarbon, alkane chain, naphthenic ring composition, molecular weight is very big, mean molecule size about 6~9nm.In structure of asphaltene also containing sulphur, nitrogen, The hetero atoms such as metal, 80%~90% metal is enriched in asphalitine in crude oil.These impurity " hide " portion in the molecule deeply, Needing could imurity-removal under harsh operating condition.Asphalitine is in the resolution ratio of hydrogenation process and the aperture of used catalyst It is related.Catalyst aperture is at least greater than 10nm, and asphalitine is possible to be diffused into catalyst duct.Catalyst also needs to have Biggish Kong Rong, to improve diffusion and accommodate more impurity.Therefore, for handling macromolecular compound, catalyst Pore structure seems most important: catalyst should have a certain number of macropores, can make table in the accessible catalyst of larger asphaltene molecule Face, to reach maximum hydrodemetallization degree.But big hole number cannot be excessive, and otherwise, specific surface area is reduced, the obvious drop of activity It is low.

CN1315994C discloses a kind of up flow type reaction system, using the catalyst layer of at least two different hydrogenation activities Up-flow reactor, not only remove metal can also remove sulphur and carbon residue.Multiple and different bed fillings are arranged in up-flow reactor The catalyst of different hydrogenation activities is used to remove the impurity such as metal, carbon residue and the sulfide in residual oil raw material.It is a variety of due to loading The catalyst of performance causes whole demetalization ability low, and there is also matched with subsequent downflow reactor catalyst performance Problem is unfavorable for performance and the long-term operation of catalyst performance.

Summary of the invention

In view of the deficiencies of the prior art, the present invention provides a kind of hydrotreating methods of heavy hydrocarbon feeds.This method makes Various function catalyst cooperations in flow reactor, down-type fixed-bed reactor, and then the whole of catalyst can be improved Body performance realizes that up flow type catalyst is synchronous with the catalytic performance of fixed bed catalyst, improves catalytic activity, extends operating week Phase.

The hydrotreating method of heavy hydrocarbon feeds of the present invention, comprising: up-flow reactor and at least one down-flow fixed bed Reactor series connection, heavy hydrocarbon feeds pass sequentially through up-flow reactor and down-type fixed-bed reactor, down-flow fixed bed reaction Device effluent is isolated to each product；A kind of following hydrorefining catalyst is at least loaded in the up flow type hydrogenator Agent；The hydrotreating catalyst includes carrier and active metal component, wherein the carrier is with two through channels Spherical shape, the overall diameter of ball is 5.0~8.0mm, and two passes pass through the centre of sphere and orthogonal through-hole, and channel diameter is ball The 30%~60% of overall diameter, preferably 30%~55%.

In hydrotreating catalyst of the present invention, the through-hole is preferably cylindrical hole.

In hydrotreating catalyst of the present invention, the active metal component includes the second metal component, that is, group VIB Metallic element and third metal component, that is, group VIII metal element.

In hydrotreating catalyst of the present invention, with Al₂O₃-SiO₂For carrier, wherein SiO₂Weight content be 35%~ 80%, preferably 40% ~ 60%.

In hydrotreating catalyst of the present invention, carrier preferably also contain the first metal component oxide, described first Metal component oxide is NiO.First metal component the oxide NiO and Al₂O₃Molar ratio be 0.03:1~0.13:1, Preferably 0.05:1~0.11:1.

In hydrotreating catalyst of the present invention, the active metal component group VIB metallic element is preferably Mo, the VIII race's metallic element is preferably Ni and/or Co.Wherein, it is counted on the basis of the weight of catalyst, the second metal component is with oxide The content of meter is 1.0%~10.0%, preferably 1.5%~6.5%, and the total content of the first metal component and third metal component is with oxygen Compound is calculated as 3.0%~10.0%, preferably 4.0%~8.0%, and the content of silica is 35.0%~55.0%, the content of aluminium oxide It is 35.0%~55.0%, the molar ratio of third metal component and the second metal component in terms of atom is 1.5:1~4.5:1.

Carrier of hydrogenating catalyst of the present invention, property are as follows: specific surface area is 80~200m²/ g, Kong Rongwei 0.80mL/g or more, preferably 0.85~1.15mL/g, 35%~60% of Kong Rongwei total pore volume shared by 20~100nm of bore dia, Average pore diameter is 18nm or more, preferably 20 ~ 30nm.

In the hydrotreating method of heavy hydrocarbon feeds of the present invention, the catalyst of down-type fixed-bed reactor filling can be this The common heavy hydrocarbons hydrotreating catalyst in field, including Hydrobon catalyst and hydrodenitrogenation catalyst.Catalyst is general Hydrobon catalyst, hydrodenitrogenation catalyst are followed successively by by the flow direction of reaction mass.Hydrobon catalyst and plus hydrogen Denitrification catalyst is typically all using porous refractory inorganic oxide such as aluminium oxide as carrier, and group VIB and/or group VIII metal are Active metal component, vib metals are W and/or Mo, and group VIII metal is Co and/or Ni, are selectively added other each The catalyst of the elements such as kind auxiliary agent such as P, Si, F, B.Currently preferred Hydrobon catalyst, using the weight of catalyst as base Standard, content of the group VIB in terms of oxide be 5.0% ~ 18.0%, content of the group VIII metal in terms of oxide be 1.5% ~ 6.0%.Currently preferred hydrodenitrogenation catalyst, on the basis of the weight of catalyst, content of the group VIB in terms of oxide It is 6.0% ~ 20.0%, content of the group VIII metal in terms of oxide is 2.0% ~ 8.0%.It is excellent in the hydrodenitrogenation catalyst One of auxiliary agent such as P, Si, B etc. or a variety of is added in choosing, and weight content in the catalyst is 10% or less.Such as China Petroleum FZC series residuum hydrodesulfurization catalyst, the denitrification catalyst of chemical inc's catalyst branch production, can also be with It is prepared according to this field existing method.

In the hydrotreating method of heavy hydrocarbon feeds of the present invention, the volume of the hydrotreating catalyst of up-flow reactor filling With the volume ratio of the Hydrobon catalyst and hydrodenitrogenation catalyst that are loaded in down-type fixed-bed reactor be 1:0.2 ~ 5.0:0.2 ~ 5.0.

The preparation method of the hydrotreating catalyst of up-flow reactor filling of the present invention, comprising:

(1) Aci-Jel solvent is added into silicon source, carries out acidification；

(2) boehmite, curing agent are added into step (1), is configured to plaster material；

(3) plaster material obtained by step (2) is added in mold, then plaster material mold heating certain time will be filled, make cream Shape material curing molding；

(4) step (3) material is deviate from into mold, washed, dry, roasting obtains catalyst carrier；

(5) by step (4) resulting vehicle dip loading catalyst activity metal component, then through drying, roasting, hydrotreating is obtained Catalyst.

In the preparation method of up-flow reactor hydrotreating catalyst of the present invention, the first gold medal is preferably introduced into carrier Belong to oxide, the first source metal (nickel source) can be introduced in step (1) and/or step (2), be preferably introduced into method specifically such as Under: nickel source is added into step (1) resulting material, and is allowed to be dissolved in material.Nickel source can use soluble nickel salt, Middle soluble nickel salt can be one or more of nickel nitrate, nickel sulfate, nickel chloride, preferably nickel nitrate.

In the preparation method of up-flow reactor hydrotreating catalyst of the present invention, silicon source described in step (1) is One or more of waterglass, silica solution, wherein mass content of the silicon in terms of silica be 20%~40%, preferably 25%~ 35%；The Aci-Jel solvent is one or more of nitric acid, formic acid, acetic acid, citric acid, preferably nitric acid, the peptized acidic The mass concentration of agent is 55%~75%, preferably 60%~65%, and Aci-Jel solvent adding amount is with mole of hydrogen ion and silica Than for 1:1.0~1:1.5；PH value after the silicon source progress acidification is 1.0~4.0, preferably 1.5~2.5.

In the preparation method of up-flow reactor hydrotreating catalyst of the present invention, step (2) is described to intend thin water aluminium The dry weight of stone is 70% or more, is converted into γ-Al through high-temperature roasting₂O₃Property afterwards is as follows: Kong Rongwei 0.95mL/g or more, It is preferred that 0.95 ~ 1.2mL/g of Kong Rongwei, specific surface area 270m²/ g or more, preferably specific surface area are 270 ~ 330m²/g.It is described solid Agent is one of urea, organic ammonium salt or a variety of, and the organic ammonium salt is preferably six methines, four ammonium.The addition of curing agent Amount is 1:1.5~1:2.0 with the molar ratio of nitrogen-atoms and silica.The solid content that is configured in plaster material is with titanium dioxide Silicon and alumina weight are calculated as 25%~45%, preferably 28%~40%, and plaster material should have the plastic of certain fluidity.

In the preparation method of up-flow reactor hydrotreating catalyst of the present invention, step (3) described mold includes Shell and three mandrels with spherical hollow space, shell select rigid, and outer shape can have any shape, preferably ball The symmetric geometries such as shape, there is that a root long degree is greater than the long mandrel of spherical hollow space diameter and two root long degree are greater than ball in three mandrels The short mandrel of shape cavity radius.The present invention is illustrated so that outer shape is spherical shape as an example, and four are respectively equipped on spherical shell Tapped through hole, wherein symmetrical as symmetrical centre using the cavity spherical shape centre of sphere in pairs, the diameter of spherical hollow space can basis The size of catalyst granules is adjusted, and can be 5.0 ~ 16.0mm.Spherical shell can be made of two identical hemispheres, It can also be made of four a quarter spheres.Long mandrel is mounted in the through-hole of spherical shell and inside spherical hollow space, Axle diameter can be adjusted according to the size in two through channel apertures in catalyst, can be the 30% of spherical hollow space diameter ~60%, preferably 30%~55%, the both ends of mandrel have screw thread, and the screw thread in thread size and housing through-hole matches, long mandrel peace Dress is fixed to make each spherical shell form sphere, and inside forms spherical hollow space, and another two short mandrels are respectively from another two tapped through hole It is inserted into and is fixed after contacting long mandrel, diameter is identical as long axle diameter.When preparation, two through-holes on shell, insertion are utilized Long mandrel makes each section spherical shell be fixed to each other, and inside becomes a complete hollow spheres, then by another short mandrel It is inserted by a through-hole of shell, is fixed after touching long mandrel, keep the last one through-hole of shell unimpeded, at this moment by paste Material is injected or is pressed into from the last one through-hole of shell, makes it full of after entire cavity, the short mandrel of last root is inserted into, is connect It is fixed after contacting long mandrel.Three mandrels vertically fixed will form orthogonal carrier channel.It is described to fill paste again Material mold heating temperature be 70~200 DEG C, preferably 100~150 DEG C, constant temperature time be 30~240 minutes, preferably 50~120 Minute.

In the preparation method of up-flow reactor hydrotreating catalyst of the present invention, due in mold in step (4) Alkaline gas is discharged after plaster material is heated, automatic demoulding after making plaster material solidify and shrink；The washing is to use deionization Water washs the spherical material after demoulding to neutrality；The drying temperature is 100~150 DEG C, and drying time is 4~10 hours. The maturing temperature is 500 ~ 900 DEG C, and preferably 550 ~ 800 DEG C, calcining time is 2~8 hours.

In the preparation method of up-flow reactor hydrotreating catalyst of the present invention, step (5) described carrier impregnation Drying and roasting condition after catalyst activity metal component is as follows: it is 4~10 hours dry at 100~150 DEG C, then 400~ 600 DEG C roast 2~6 hours.

In heavy-hydrocarbon raw material hydrogenation treatment method of the invention, using at least one up flow type hydrogenator, it can be set Multiple up flow type hydrogenator tandem process also can be set in one up flow type hydrogenator, general setting one or two A up flow type hydrogenator.Hydrotreating catalyst of the invention is preferably loaded in the up flow type hydrogenator, preferably Using at least two catalyst beds, and each catalyst bed loads same hydrotreating catalyst of the present invention.

In the hydrotreating method of heavy hydrocarbon feeds of the present invention, one up-flow reactor is preferably provided with 2 ~ 5 catalysis Agent bed, each catalyst bed preferably use the same hydrotreating catalyst of the present invention.Each bed height can in reactor Appropriate adjustment.When two catalyst beds are arranged in one up flow type hydrogenator, lower part is the first bed, top the Two beds, wherein the first bed accounts for 35%~50% of catalyst total fill able volume in the up-flow reactor, the second bed accounts for this The 50%~65% of catalyst total fill able volume in up-flow reactor.Three catalysis are arranged in one up flow type hydrogenator When agent bed, lower part is the first bed, and middle part is the second bed, and top is third bed, and the first bed accounts for up flow type reaction The 20%~30% of catalyst total fill able volume in device, the second bed account for catalyst total fill able volume in the up-flow reactor 25%~35%, third bed accounts for 30%~45% of catalyst total fill able volume in the up-flow reactor.According to what is processed raw material Difference, bed height can be set identical, can also be different.

In the hydrotreating method of heavy hydrocarbon feeds of the present invention, the operating condition that up flow type hydrogenator uses is as follows: anti- Answer 8 ~ 25MPa of pressure, 350 ~ 420 DEG C of reaction temperature, the hydrogen to oil volume ratio (ratio under standard state of up-flow reactor entrance Value, similarly hereinafter) it is 150: 1 ~ 350: 1,0.1 ~ 2.0h of volume space velocity when liquid^-1。

In the hydrotreating method of heavy hydrocarbon feeds of the present invention, down-type fixed-bed reactor can be arranged in series 1 ~ 5, excellent Select 2 ~ 3.It can according to need the one or more catalyst beds of setting in each down-type fixed-bed reactor.

In the hydrotreating method of heavy hydrocarbon feeds of the present invention, the operating condition that down-type fixed-bed reactor uses is as follows: 8 ~ 25MPa of reaction pressure, 360 ~ 430 DEG C of reaction temperature, hydrogen to oil volume ratio 500: 1 ~ 1200: 1, volume space velocity 0.2 when liquid ~ 1.0h^-1。

In the hydrotreating method of heavy hydrocarbon feeds of the present invention, down-type fixed-bed reactor effluent is isolated to each production Object, product includes light hydrocarbons, naphtha cut, diesel oil distillate and tower bottom oil, wherein separation can be carried out using conventional method, For example detailed process can be with are as follows: down-type fixed-bed reactor effluent carries out gas-liquid separation first, and obtained gas phase is mainly Hydrogen, the liquid phase obtained after hydrogenation reaction effluent gas-liquid separation enter low pressure separator, obtain lightweight subsequently into fractionating column Hydro carbons and naphtha cut, diesel oil distillate and tower bottom oil, the hydrogen wherein obtained after gas-liquid separation can be handled by depriving hydrogen sulphide Circulation is used for hydrogenation reaction afterwards, and hydrogenation process also can according to need the new hydrogen of supplement.

Compared with the prior art, the advantages of the present invention are as follows:

1, at least have unique shape and pore structure using a kind of present invention in up flow type hydrotreating reactor of the invention Hydrotreating catalyst, not only mechanical strength with higher and wear-resisting property, but also have a characteristic that (1) has Good diffusion admittance and reaction channel, can eliminate the influence of diffusion couple reaction, and keep reaction more efficient, and catalyst utilizes Effect is more preferable；(2) there is good anti-coking and bed thermal stability；(3) has good Hydrogenation；(4) have good Demetalization impurity ability, while also with the ability of certain desulfurization nitrogen and carbon residue impurity.

2, it using the method for the present invention, preferably in up flow type hydrogenator, loads identical hydrotreating of the present invention and urges Agent, due to the direction along reaction stream, material properties gradually improves, and hydrogenation reaction is exothermic reaction, and reaction temperature can be by Step improves, and rear portion catalyst bed is under the less environment of amounts of hydrogen in entire reaction process, low using large aperture The up flow type catalyst of consumption hydrogen is conducive to the stabilization of catalyst bed and the performance of catalyst performance.In addition, along reaction stream Orienting response temperature steps up, if in the higher reaction zone of temperature, using the catalyst of greater activity, it is easier to cause bed The scarce hydrogen reaction of layer part, is easy to cause the generation of bed hot spot and the fluctuation of bed.Therefore, up-flow reactor can be led to The control of catalyst activity is crossed, can realize the balance of activity and stability.

3, in up flow type hydrogenator, although being in strong back-mixing state not as good as material in fluidized bed reactor.But Since its logistics flows to the microdilatancy state of feature and catalyst bed, if using in fixed bed hydrogenation technology in same catalysis Agent bed uses different catalysts gradation technology, the fluctuation of Yi Yinqi bed back-mixing and bed reaction, the stable operation to device Have an adverse effect.

4, up flow type hydrotreating catalyst of the invention has the good de- ability for holding metal, has benefited from the excellent of catalyst The optimization of the drill way layout and carrier structure of change, the catalyst in addition to having higher hydrogenation capability, meanwhile, have certain de- Metal, desulfurization and carbon residue and asphalitine conversion capability, therefore the catalyst has the characteristics that long-period stable operation.

5, in the method for the present invention, up-flow reactor loading catalyst removes metal ability and protrudes, and is conducive to device long week Phase stable operation.Down-type fixed-bed reactor all loads high activity hydrogenation and desulphurization, hydrodenitrogenation catalyst, can be improved miscellaneous The deep hydrogenation conversion capability of matter.Therefore, the method for the present invention makes full use of up-flow reactor and down-type fixed-bed reactor Reaction characteristics up-flow reactor, the various function catalyst cooperations of down-type fixed-bed reactor are further increased The effect of combined process flow hydrogenation plant coordinated, solve cannot achieve when two kinds of reactors combine catalyst catalytic performance it is same Step and the deficiency for effectively extending operation cycle, the Temperature Distribution of down-type fixed-bed reactor is more reasonable, has given full play to and has flowed down The performance of formula fixed bed reactor catalyst, improves catalyst utilization, improves the removal efficiency of impurity and further improves Product quality reduces the shut-down more catalyst changeout number of device, hence it is evident that improve the economic benefit of device.

Detailed description of the invention

Fig. 1 is process flow diagram of the invention；

Fig. 2 is the process flow diagram of the embodiment of the present invention；

Fig. 3 is the diagrammatic cross-section of carrier of hydrogenating catalyst preparation process of the present invention；

1 description of symbols of attached drawing is as follows:

11. heavy hydrocarbon feeds；12 hydrogen；13 up-flow reactors；14 up flow type hydrogenation reaction effluents；15 mixed hydrogen；16 fixed beds One is anti-；17 generate oil；18 mixed hydrogen；19 fixed beds two are anti-；110 reaction mixtures；111 separators；112 recycle hydrogens；113 hydrogenation liquids Phase product；114 pressure fractionating towers；115 light hydrocarbon gas；116 light naphtha fractions；117 heavy naphtha fractions；118 diesel oil distillates； 119 tower bottom residual oil；120 compressors；122 new hydrogen；

The description of symbols of attached drawing 2 and 3 is as follows:

1. mould housing；2. plaster material；3. long mandrel；4. short mandrel；5. through channel.

Specific embodiment

Below with reference to embodiment, the technical scheme of the present invention will be explained in further detail, but embodiment is not intended to limit this The protection scope of invention.In the present invention, wt% is mass fraction.

In the present invention, the specific surface area, Kong Rong, aperture and pore size distribution are measured using low temperature liquid nitrogen absorption method.

Method provided by the present invention is further detailed with reference to the accompanying drawing, but does not therefore limit this hair It is bright.

Enter as shown in Figure 1, heavy hydrocarbon feeds 11 enter after mixing with hydrogen 12 from the bottom of up-flow reactor 13, Hydrotreating reaction is carried out in the presence of up flow type hydrogenation catalyst, up flow type hydrogenation reaction effluent 14 enters down-flow fixed bed Reactor, reaction stream is that the type of flow from top to bottom exists in fixed bed residual oil hydrocatalyst in fixed bed reactors Lower carry out hydrotreating.Up flow type hydrogenation reaction effluent 14 initially enters one anti-16 top of fixed bed, an anti-hydrogenated oil 17 are mixed into two anti-19 top of fixed bed with mixed hydrogen 18, and reaction mixture 110 obtains recycle hydrogen through 111 separating-purifying of separator 112 and hydrogenation liquid phase product 113, wherein hydrogenation liquid phase product 113 enter the fractionation of atmospheric fractional tower 114 obtain light hydrocarbon gas 115, Light naphtha fraction 116, heavy naphtha fraction 117, diesel oil distillate 118 and tower bottom residual oil 119.Recycle hydrogen 112 passes through compressor 120 mixed with new hydrogen 122 after for each reactor, the distribution of hydrogen is true by the requirements such as reaction condition and temperature of reactor control It is fixed.

As shown in Fig. 2, the mold includes to have spherical hollow space when the present invention prepares catalyst for hydrotreatment of residual oil carrier Shell 1, a root long mandrel 3 and two short mandrel 4.The present invention is illustrated so that outer shape is spherical shape as an example.Spherical shell 1 On be respectively equipped with four tapped through holes, wherein symmetrical as symmetrical centre using the cavity spherical shape centre of sphere in pairs, spherical hollow space Diameter be D₁.Spherical shell 1 is made of two identical hemispheres.Mandrel 3 is mounted in the through-hole of spherical shell 1 simultaneously Inside spherical hollow space, long 3 diameter of mandrel is d₁, long 3 length of mandrel is greater than spherical hollow space diameter, and the both ends of mandrel are with spiral shell Screw thread in line, thread size and housing through-hole matches, and the long installation of mandrel 3, fixation make two hemisphere spherical shells 1, internal Spherical hollow space is formed, another two short mandrel 4 is inserted into from another two tapped through hole respectively, and axle diameter is identical as long mandrel 3, short core 4 length of axis is greater than spherical hollow space radius, fixed after short mandrel 4 touches long mandrel 3.

When preparing catalyst for hydrotreatment of residual oil, using the tapped through hole on spherical shell 1, it is inserted into long mandrel 3 and passes through Wear inside spherical hollow space, the installation of long mandrel 3, it is fixed make two hemisphere spherical shells 1, inside forms spherical hollow space, then will Another short mandrel 4 is inserted by a through-hole of shell, is fixed after touching long mandrel 3, is kept the last one through-hole of shell It is unimpeded, at this moment plaster material 2 is pressed into from the last one through-hole of spherical shell 1, after so that it is full of entire cavity, by last The short mandrel 4 of root is inserted into, and is fixed after touching long mandrel 3.Three mandrels vertically fixed will form orthogonal through channel 5, such as Fig. 3.

Embodiment 1

It weighs the waterglass 1000g that silica content is 30wt% to be added in beaker, starts agitating device, slowly add into beaker Enter the nitric acid solution 376g that mass concentration is 62%, make the pH value 2.0 of water glass solution in beaker, then adds into above-mentioned solution Entering 416.7g boehmite, (property is as follows: Kong Rong 0.985mL/g, specific surface area 313m²/ g, butt 72wt%), stirring Curing agent urea 83g is added after uniformly, deionized water is added after urea all dissolution, making material in beaker is in certain The paste of mobility, and the solid content in terms of silica and aluminium oxide is 33%.

Above-mentioned plaster material is pressed into the rigid mould well prepared in advance with spherical hollow space and mandrel, plaster material After entire cavity, the short mandrel of last root is inserted into, it is fixed after short mandrel contacts first mandrel.Two vertical fixed Mandrel will form orthogonal carrier channel.

Plaster material mold will be filled and heat most 120 DEG C, constant temperature 60 minutes, due in mold plaster material it is heated after release Automatic demoulding becomes spherical gel after putting ammonia plaster material being made to solidify and shrink, then spherical gel is washed with deionized into Property, it is 5 hours dry at 120 DEG C, it is roasted through 600 DEG C and obtains within 3 hours spherical catalyst carrier A of the present invention, gained catalyst carries The overall diameter of body A is about 5.5mm, and through-hole diameter is about 2.5mm.

Carrier A is impregnated into Mo-Ni-P solution, it is 6 hours dry at 120 DEG C, it is roasted 3 hours through 500 DEG C and obtains the present invention Catalyst A_C, catalyst property is shown in Table 1.

Embodiment 2

Preparation process such as embodiment 1, only more mold exchange increase the diameter of cavity and mandrel, the catalyst carrier B of preparation and urge Agent B_CProperty is shown in Table 1.Wherein, the overall diameter of gained catalyst carrier B is about 7.5mm, and through-hole diameter is about 3.8mm.

Embodiment 3

Preparation process such as embodiment 1 will only be slowly added to nitric acid solution 373g and 53g of the mass concentration for 62% into beaker Nickel nitrate, and the solid content in terms of silica and aluminium oxide is 35%, the catalyst carrier C and catalyst C of preparation_C, property It is shown in Table 1.Wherein, the overall diameter of gained catalyst carrier C is about 5.5mm, and through-hole diameter is about 2.5mm.

Comparative example 1

It weighs the waterglass 1000g that silica content is 30% to be added in beaker, starts agitating device, be slowly added into beaker Concentration is 62% nitric acid solution 376g, makes the pH value 2.0 of water glass solution in beaker, then adding hole is held into above-mentioned solution 0.985mL/g, specific surface area 313m²/ g, the boehmite 416.7g that butt is 72%, adds solidification after mixing evenly Deionized water is added after urea all dissolution in agent urea 83g, and making material in beaker is in the paste with certain fluidity, and The concentration of the sum of silica and aluminium oxide is 33%.

Above-mentioned plaster material is pressed into the rigid mould of the identical hemispherical hollow structure of two diameters, spherical hollow space Diameter is with the spherical hollow space diameter of 1 mould therefor of embodiment, then that two hemispherical molds are squeezed synthesis one is spherical；

Plaster material mold will be filled and heat most 120 DEG C, constant temperature 60 minutes, due in mold plaster material it is heated after discharge ammonia Automatic demoulding becomes spherical gel after gas makes plaster material solidify and shrink, then spherical gel is washed with deionized to neutrality, It is 5 hours dry at 120 DEG C, it is roasted 3 hours through 600 DEG C and obtains this comparative example spherical catalyst carrier D, gained catalyst carrier The overall diameter of D is about 5.5mm.

Carrier D is impregnated into Mo-Ni-P solution, dry 6 hours at 120 DEG C, is roasted through 500 DEG C and obtains within 3 hours comparing Example catalyst D_C, catalyst property is shown in Table 1.

Embodiment 4

In the present embodiment, a up-flow reactor and three down-type fixed-bed reactors, three reactors all positions are set In up-flow reactor downstream, it is sequentially connected in series use.Up flow type hydrogenated oil passes sequentially through three fixations after mixing with mixed hydrogen Bed reactor.

Single catalyst bed is arranged in up-flow reactor, and loading catalyst total amount is 300mL.Up-flow reactor difference Using up flow type hydrotreating catalyst A_C、B_C、C_CAnd D_C,.Three fixed bed reactors are single catalyst bed.

Raw materials used is typical Middle East residual oil, hydro-upgrading reaction is carried out in up flow type residual hydrogenation reactor, mainly Up flow type hydrogenated oil is obtained after removing metal impurities.Fixed bed includes three reactors, an anti-filling desulphurization catalyst FZC-34A 170 mL of 200 mL, two anti-filling desulphurization catalyst FZC-34A130 mL and denitrification catalyst FZC-41A, three is anti- The property of filling denitrification catalyst FZC-41A300 mL, desulphurization catalyst FZC-34A and denitrification catalyst FZC-41A are shown in Table 2. Fixed bed hydrogenation reaction, which is obtained, by further hydrotreating generates oil.See Table 3 for details for technological condition.Up-flow reactor institute The property of hydrogenated oil obtained by hydrogenated oil and downflow reactor is shown in Table 4, wherein Ac (on), Bc (on), Cc (on) With Dc (on) refer to up flow type hydrogenated oil, Ac (under), Bc (under), Cc (under) and Dc (under) refer to that down-flow fixed bed is hydrogenated to Oil.

Embodiment 5

With embodiment 4, wherein up-flow reactor uses hydrotreating catalyst A_C, and use two catalyst beds, body Product is than being 1:1.The property of reaction products therefrom is shown in Table 5.

Comparative example 2

In this comparative example, a up-flow reactor and three down-type fixed-bed reactors, each reactor are equally set Volume is identical.

Up flow type hydrogenator is arranged using bunk beds as different from Example 5, and two bed volumes are identical, 150mL catalyst is loaded, loads up flow type hydrogenation catalyst FZC10UH and FZC11UH respectively.FZC10UH belongs to conventional upper Streaming catalyst for demetalation, FZC11UH belong to the up flow type hydrodemetallization desulphurization catalyst of high activity, and catalyst property is shown in Table 2.Hydrogenation products obtained by up-flow reactor carry out adding at hydrogen in the presence of fixed bed residual oil hydrocatalyst after mixing with hydrogen Reason reaction, fixed bed includes three reactors, main to load catalyst for demetalation FZC-28A, admission space 200ML；Desulfurization Catalyst FZC-34A, admission space 200ML；Denitrification catalyst FZC-41A, admission space 400ML.By further adding Hydrogen handles to obtain fixed bed hydrogenation reaction generation oil.See Table 3 for details for technological condition, and the property for reacting products therefrom is shown in Table 5.

The property of table 1 embodiment and comparative example prepared catalyst

Catalyst carrier number	Carrier A	Carrier B	Support C	Carrier D
					Kong Rong, mL/g	0.771	0.772	0.769	0.76
Specific surface area, m2/g	140	142	137	151
					Average pore diameter, nm	22.1	21.8	22.5	20.1
Pore size distribution, %
					<8.0nm	0.8	0.9	0.9	1.2
8-20 nm	62.4	62.4	62.4	63.6
					>20.0nm	36.8	36.7	36.7	35.2
Catalyst number	Catalyst AC	Catalyst BC	Catalyst CC	Catalyst DC
					Tenor, %
MoO3	7.3	8.3	7.2	7.4
					NiO	2.2	2.2	3.1	2.3
Side pressure strength, N/	31	45	40	87

The property of 2 comparative example hydrogenation catalyst used therein of table

The catalyst trade mark	FZC-28A	FZC-34A	FZC-41A	FZC-10U	FZC-11U
						Function	Catalyst for demetalation	Desulphurization catalyst	Denitrification catalyst	Catalyst for demetalation	Desulphurization catalyst
Grain shape	2-8mm bar shaped	2-8mm bar shaped	2-8mm bar shaped	It is spherical	It is spherical
						Particle outer diameter, mm	1.55	1.20	1.3	2.9	2.9
Intensity, N.mm-1	16	20	26	32	30
						Specific surface area, m2/g	133	182	228	110	148
Wear rate, wt%	1.32	0.92	0.76	0.3	0.4
						Tenor, wt%
MoO3	7.83	12.67	18.70	5.2	10.8
						NiO	2.04	3.95	4.32	1.2	2.4

3 embodiment of table and comparative example prevailing operating conditions

Project	Embodiment 4	Embodiment 4	Embodiment 4	Embodiment 4	Embodiment 5	Comparative example 2
							Up flow type catalyst number	AC	BC	CC	DC	AC/AC	FZC10UH and FZC11UH
One anti-inlet pressure, MPa	15.7	16.2	15.7	15.7	15.7	15.7
							Total volume air speed, h-1	0.19	0.19	0.19	0.19	0.19	0.19
UFR reactor operating condition
							Volume space velocity, h-1	0.50	0.50	0.50	0.50	0.50	0.50
Entrance gas-oil ratio	270	300	270	270	270	270
							Inlet temperature, DEG C	375	373	375	375	375	375
Outlet temperature, DEG C	395	394	394	392	393	398
							Mean temperature, DEG C	385	384	385	384	384	387
Down-type fixed-bed reactor operating condition
							Volume space velocity, h-1	0.3125	0.3125	0.3125	0.3125	0.31125	0.3125
Entrance gas-oil ratio	600	600	600	600	600	600
							Mean temperature, DEG C	395	394	395	394	395	392
The each reactor Distribution of temperature rise of fixed bed
							One anti-temperature rise, DEG C	12	12	11	10	11	7
Two anti-temperature rises, DEG C	20	21	18	19	19	19
							Three anti-temperature rises, DEG C	15	14	15	15	15	13

The raw materials used, up flow type of 4 embodiment of table 4 and fixed bed hydrogenation generate the main character of oil

	Raw material	Ac (on)	Ac (under)	Bc (on)	Bc (under)	Cc (on)	Cc (under)	Dc (on)	Dc (under)
										S, wt%	3.15	1.25	0.42	1.32	0.45	1.29	0.45	1.47	0.50
N, μ g/g	3422	2260	1302	2283	1369	2278	1351	2330	1387
										Carbon residue (CCR), wt%	12.75	7.60	4.30	7.83	4.60	7.78	4.45	8.22	5.30
Density (20 DEG C), kg/m3	986.10	955.0	935.6	955.9	935.7	955.8	936.2	959.7	938.8
										Viscosity (100 DEG C), mm2/s	130.90	41.51	27.6	42.57	29.96	42.32	29.2	48.30	32.35
Ni+V, μ g/g	78.20	22.60	12.20	21.60	12.06	23.10	12.53	26.74	13.78

5 embodiment 5 of table and comparative example 2 is raw materials used, up flow type and fixed bed hydrogenation generate oily main character

		Embodiment 5	Embodiment 5	Comparative example 2	Comparative example 2
						Project	Raw material	Up flow type hydrogenated oil	Fixed bed hydrogenation residual oil	Up flow type hydrogenated oil	Fixed bed hydrogenation residual oil
S, wt%	3.15	1.26	0.43	1.55	0.52
						N, μ g/g	3422	2262	1323	2280	1830
Carbon residue (CCR), wt%	12.24	7.58	4.22	8.12	5.65
						Density (20 DEG C), kg/m3	986.10	955.6	935.5	957.4	940.00
Viscosity (100 DEG C), mm2/s	130.90	41.62	27.2	47.51	36.30
						Ni+V, μ g/g	78.20	22.78	13.33	33.50	14.83

Embodiment 6

Residual hydrogenation stability test test, in order to further investigate the stability of technology of the invention, respectively to above-mentioned Embodiment 5 and comparative example 2 have carried out stability life test, and reaction result is shown in Table 6.

6 residual hydrogenation stability test of table

Project/the duration of runs	Catalyst	Up flow type generates oil/fixed bed and generates oil	500h	1000h	3000h	5000h	6000h	7000h	Fixed bed generates oil product index
										Generate oil S, wt%	Embodiment 5	Up flow type generates oil	1.26	1.26	1.28	1.30	1.31	1.33
Generate oil S, wt%	Embodiment 5	Fixed bed generates oil	0.43	0.43	0.45	0.46	0.46	0.48	≤0.60
										Generate oil S, wt%	Comparative example 2	Up flow type generates oil	1.55	1.58	1.67	1.76	1.89	1.96
Generate oil S, wt%	Comparative example 2	Fixed bed generates oil	0.52	0.53	0.54	0.58	0.66	0.71	≤0.60
										Generate oil CCR, wt%	Embodiment 5	Up flow type generates oil	7.57	7.60	7.63	7.77	7.84	7.88
Generate oil CCR, wt%	Embodiment 5	Fixed bed generates oil	4.22	4.25	4.26	4.30	4.35	4.40	≤6.0
										Generate oil CCR, wt%	Comparative example 2	Up flow type generates oil	8.12	8.57	8.96	9.39	9.72	9.94
Generate oil CCR, wt%	Comparative example 2	Fixed bed generates oil	5.65	5.68	5.73	5.88	5.92	6.42	≤6.0
										Generate oily (Ni+V), μ g/g	Embodiment 5	Up flow type generates oil	22.76	22.85	23.20	23.35	24.55	25.88
Generate oily (Ni+V), μ g/g	Embodiment 5	Fixed bed generates oil	13.32	13. 48	13.52	13.85	13.95	14.25	≤16.00
										Generate oily (Ni+V), μ g/g	Comparative example 2	Up flow type generates oil	33.45	33.70	35.62	36.34	37.93	40.3
Generate oily (Ni+V), μ g/g	Comparative example 2	Fixed bed generates oil	14.83	14.87	15.02	15.58	15.97	17.35	≤16.00

2 up flow type catalyst inactivation fast speed of comparative example as shown in Table 6, by 6000 hours since up flow type inactivation is comparatively fast made Integral performance is insufficient, and it is 0.66% that fixed bed, which generates oily sulfur content, the requirement beyond index 0.60；Equally it is embodied in carbon residue Removing, was significantly increased at oily carbon residue to 9.94% by 7000 hours due to up flow type, fixed bed catalyst performance is difficult to make up The active loss of up flow type, it is 6.42% that fixed bed, which generates oily carbon residue content, the requirement beyond index 6.00%.Equally it is embodied in gold The removing for belonging to (Ni+V), increased to 40.3 μ g/g at oily metal (Ni+V) due to up flow type by 7000 hours, fixed bed is at oil Metal (Ni+V) is more than 17 μ g/g, the requirement beyond 16.00 μ g/g of index.The up flow type performance of embodiment 5 is prominent, even if arriving Still good stability is shown within 7000 hours, preferable with fixed bed catalyst Performance Match, final fixed bed generates oil Sulfur content is 0.48%, carbon residue 4.40, and metal (Ni+V) is less than 15 μ g/g.Therefore, the present invention compares as can be seen from Table 6 Generation oil nature compared with prior art in example has and is obviously improved, and the present invention than comparative example hydrogenation activity and stability more It is good, the service life of catalyst can be extended.

Claims (20)

1. a kind of hydrotreating method of heavy hydrocarbon feeds, comprising: up-flow reactor is reacted at least one down-flow fixed bed Device series connection, heavy hydrocarbon feeds pass sequentially through up-flow reactor and down-type fixed-bed reactor, down-type fixed-bed reactor stream Object is isolated to each product out；A kind of following hydrotreating catalyst is at least loaded in the up flow type hydrogenator；Institute The hydrotreating catalyst stated includes carrier and active metal component, wherein the carrier is the ball with two through channels Shape, the overall diameter of ball are 5.0~8.0mm, and two passes pass through the centre of sphere and orthogonal through-hole, and channel diameter is straight outside ball The 30%~60% of diameter, preferably 30%~55%.

2. the method as described in claim 1, which is characterized in that in the hydrotreating catalyst, the through-hole is circle Cylindricality through-hole.

3. the method as described in claim 1, which is characterized in that in the hydrotreating catalyst, with Al₂O₃-SiO₂To carry Body, wherein SiO₂Weight content is 35%~80%, preferably 40% ~ 60%.

4. method as claimed in claim 3, which is characterized in that in the carrier of hydrogenating catalyst, also contain first Metal component oxide, the first metal component oxide are NiO.

5. method as claimed in claim 4, which is characterized in that in the carrier of hydrogenating catalyst, the first metal group Sub-oxide NiO and Al₂O₃Molar ratio be 0.03:1~0.13:1, preferably 0.05:1~0.11:1.

6. the method as described in claim 1-5 any one, which is characterized in that in the carrier of hydrogenating catalyst, The property of carrier is as follows: specific surface area is 80~200m²/ g, Kong Rongwei 0.80mL/g or more, preferably 0.85~1.15mL/g, hole The 35%~60% of Kong Rongwei total pore volume shared by 20~100nm of diameter, average pore diameter are 18nm or more, preferably 20 ~ 30nm.

7. the method as described in claim 1, which is characterized in that the hydrotreating catalyst, active metal component include Second metal component, that is, group VIB metallic element and third metal component, that is, group VIII metal element, wherein group VIB metal Element is preferably Mo, and group VIII metal element is preferably Ni and/or Co.

8. the method for claim 7, which is characterized in that in the hydrotreating catalyst, with the weight of catalyst On the basis of count, content of second metal component in terms of oxide be 1.0%~10.0%, preferably 1.5%~6.5%, the first metal The total content of component and third metal component is calculated as 3.0%~10.0%, preferably 4.0%~8.0% with oxide, and silica contains Amount is 35.0%~55.0%, and the content of aluminium oxide is 35.0%~55.0%, and third metal component and the second metal component are with atom The molar ratio of meter is 1.5:1~4.5:1.

9. the method as described in claim 1, which is characterized in that the catalyst of down-type fixed-bed reactor filling includes adding hydrogen Desulphurization catalyst and hydrodenitrogenation catalyst, wherein Hydrobon catalyst and hydrodenitrogenation catalyst are inorganic with porous refractory Oxide is carrier, and group VIB and/or group VIII metal are active metal component, wherein vib metals are W and/or Mo, Group VIII metal is Co and/or Ni, preferably addition auxiliary agent, wherein one or more of auxiliary agent P, Si, F, B.

10. method as claimed in claim 9, which is characterized in that the Hydrobon catalyst is with the weight of catalyst Benchmark, content of the group VIB in terms of oxide be 5.0% ~ 18.0%, content of the group VIII metal in terms of oxide be 1.5% ~ 6.0%；The hydrodenitrogenation catalyst, on the basis of the weight of catalyst, content of the group VIB in terms of oxide be 6.0% ~ 20.0%, content of the group VIII metal in terms of oxide is 2.0% ~ 8.0%；It is preferably added in the hydrodenitrogenation catalyst One of auxiliary agent such as P, Si, B is a variety of, and weight content in the catalyst is 10% or less.

11. method as claimed in claim 9, which is characterized in that the body of the hydrotreating catalyst of up-flow reactor filling The long-pending volume ratio with the Hydrobon catalyst and hydrodenitrogenation catalyst that are loaded in down-type fixed-bed reactor be 1:0.2 ~ 5.0:0.2 ~ 5.0.

12. the method as described in claim 1, which is characterized in that in one up flow type hydrogenator at least there are two Catalyst bed, and each catalyst bed loads the same hydrotreating catalyst.

13. method as claimed in claim 12, which is characterized in that one up flow type hydrogenator is arranged 2 ~ 5 and urges Agent bed, each catalyst bed is using the same hydrotreating catalyst.

14. the method as described in claim 1,12 or 13, which is characterized in that one up flow type hydrogenator setting two When a catalyst bed, lower part is the first bed, and top is the second bed, is urged wherein the first bed accounts in the up-flow reactor The 35%~50% of agent total fill able volume, the second bed account for catalyst total fill able volume in the up-flow reactor 50%~ 65%。

15. the method as described in claim 1,12 or 13, which is characterized in that one up flow type hydrogenator setting three When a catalyst bed, lower part is the first bed, and middle part is the second bed, and top is third bed, and the first bed accounts for the upstream The 20%~30% of formula catalyst in reactor total fill able volume, the second bed accounts for catalyst total fill able body in the up-flow reactor Long-pending 25%~35%, third bed account for 30%~45% of catalyst total fill able volume in the up-flow reactor.

16. the method as described in claim 1, which is characterized in that the operating condition that the up flow type hydrogenator uses is such as Under: 8 ~ 25MPa of reaction pressure, 350 ~ 420 DEG C of reaction temperature, the hydrogen to oil volume ratio of up-flow reactor entrance is 150: 1 ~ 350: 1,0.1 ~ 2.0h of volume space velocity when liquid^-1。

17. the method as described in claim 1, which is characterized in that the down-type fixed-bed reactor is arranged in series 1 ~ 5, It is preferred that 2 ~ 3.

18. the method as described in claim 1, which is characterized in that the operating condition that the down-type fixed-bed reactor uses It is as follows: 8 ~ 25MPa of reaction pressure, 360 ~ 430 DEG C of reaction temperature, hydrogen to oil volume ratio 500: 1 ~ 1200: 1, volume space velocity when liquid 0.2~1.0h^-1。

19. the method as described in claim 1, which is characterized in that down-type fixed-bed reactor effluent is isolated to respectively Product, including light hydrocarbons, naphtha cut, diesel oil distillate and tower bottom oil.

20. the method as described in claim 1 or 19, which is characterized in that the separation of down-type fixed-bed reactor effluent Journey are as follows: down-type fixed-bed reactor effluent carries out gas-liquid separation first, and obtained gas phase is hydrogen, hydrogenation reaction effluent The liquid phase obtained after gas-liquid separation enters low pressure separator, obtains each product subsequently into fractionating column, product includes light hydrocarbons And naphtha cut, diesel oil distillate and tower bottom oil, the hydrogen wherein obtained after gas-liquid separation recycle after depriving hydrogen sulphide is handled For hydrogenation reaction.