CN104593074B

CN104593074B - A kind of high melting-point wax hydrogenation method

Info

Publication number: CN104593074B
Application number: CN201310532444.5A
Authority: CN
Inventors: 袁平飞; 王士新; 王咏芳
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2013-11-04
Filing date: 2013-11-04
Publication date: 2016-07-27
Anticipated expiration: 2033-11-04
Also published as: CN104593074A

Abstract

The present invention relates to a kind of high melting-point wax hydrogenation method, including following content: wax material enters hydrotreatment reaction zone, contacts with Hydrobon catalyst and catalyst for hydro-upgrading A successively and carries out hydrogenation reaction；Hydrotreatment reaction effluent enters hydro-upgrading reaction zone, successively with catalyst for hydro-upgrading B and contacting with Hydrobon catalyst, carries out hydrogenation reaction, and hydrofinishing effluent obtains product through air stripping.Present invention process method, technical process is reasonable, the color of products obtained therefrom, stability and smell the character such as taste and all can meet requirement.

Description

A kind of high melting-point wax hydrogenation method

Technical field

The present invention relates to a kind of wax hydrofinishing process, be specially a kind of high melting-point wax hydrogenation method.

Background technology

Along with the increase of paraffin demand and kind, and paraffinic base crude oil shortage of resources, yield and the proportion of high melting point paraffin are greatly improved in recent years.High melting point paraffin is used widely in specific field so that its fusing point is higher.

The production process of current high melting point paraffin has several: by oil vacuum distillate or through deasphalting decompression residuum, first obtains refined oil through furfural treatment, obtains waxy stone then through benzol-kentone dewaxing, and then hydrofinishing or clay-filtered obtaining refine wax.Or the hydrotreatment of furfural refining oil elder generation, then benzol-kentone dewaxing respectively obtains lubricating oil and refining wax.

With conventional 56^#～58^#Paraffin compares, it is however generally that the color of high melting point paraffin, stability and to smell the characteristic of the aspects such as taste slightly inferior.In previous process, worst with the quality of clay-filtered wax；When adopting high-pressure hydrogenation, wax product quality is better.After wherein, the problem that taste is bigger is smelt in the existence of ketone benzene wax.

Due to constantly proposing and perfect of environmental regulation, the raising of pertroleum wax standard, the requirement of Quality of Paraffin Waxes is also being improved.The high melting point paraffin product obtained according to existing technique can not meet prescription sometimes, smells taste problem such as rear ketone benzene wax.

The poor reason of high melting point paraffin characteristic is many-sided, one be solvent contained therein (toluene, benzene, butanone) and oxidation impurities more, two is that aromatic hydrocarbons contained therein, nonhydrocarbon and colloid are more.

In modern lubricating oil-paraffin production technology, benzol-kentone dewaxing is the critical process that paraffin produces.When processing high melting point paraffin, owing to bigger solvent ratio and relatively low ketone ratio must be adopted, result in toluene level in thick product relatively many.Solvent make consumption more then its to recycle frequency relatively big, add the catalytic action of the assorted microgranules of machine such as ferrum in system, the probability of solvent oxidation condensation is greatly increased.And prior paraffin production technology adopts steam stripped mode remove toluene, then helpless far above the solvent oxidation product of toluene for boiling point, the impurity such as dimethylbenzene, trimethylbenzene, hexanone, heptanone, octanone etc. of higher being likely to be introduced by solvent is also helpless.And in general hydrorefining paraffin wax process, restriction due to catalyst performance, technological parameter and chemical equilibrium, the removal of trace solvent is relatively difficult, and some solvent condensation product (the condensation product 5-methyl-4-heptenyl-3-ketone such as butanone) is then more difficult to remove.If wax is to produce through positive sequence (namely also through furfural treatment before benzol-kentone dewaxing), wherein there may also be the oxide of furfural and furfural.The oxide of furfural has deeper color, it is difficult to remove.Formerly wax oil cut fraction hydrogenation is processed, then in the lubricating oil of benzol-kentone dewaxing and wax production technology, owing to the rear portion of benzol-kentone dewaxing operation does not have hydrogenation process, solvent and impurity particularly oxidation impurities in wax are more, and not easily Ex-all causes wax product to smell taste bigger.Hargil is adopted to supplement post processing also without remarkable result.

On the other hand, the boiling range of high melting point paraffin is heavier, and the content of isohydrocarbon therein, cycloalkane and aromatic hydrocarbon and colloid is of a relatively high.In modern hydrorefining paraffin wax technique, aromatic hydrocarbon therein particularly condensed-nuclei aromatics can be reduced to minimum degree by the hydrofinishing of routine paraffin wax.But being as boiling range to improve, the number of rings of cycloalkane and aromatic hydrocarbon increases, the difficulty increase that condensed-nuclei aromatics internal ring open loop is saturated with hydrogenation, in fact it could happen that the Partial hydrogenation of aromatic hydrocarbons.Although condensed-nuclei aromatics reduces more during hydrogenation, but total aromatic hydrocarbons amount is likely to reduce less.Even if adopting high-pressure hydrogenation to process technique, when boiling range is higher, it is possible to there is a degree of hydrogenation deficiency.The combined factors of above two aspects, it would be possible to be enough to have influence on the color of product, stability and smell the character such as taste.

Summary of the invention

For the deficiencies in the prior art, the present invention provides a kind of high melting-point wax hydrogenation method, present invention process method, and technical process is reasonable, the color of products obtained therefrom, stability and smell the character such as taste and all can meet requirement.

The present invention relates to a kind of high melting-point wax hydrogenation method, including following content: wax material enters hydrotreatment reaction zone, contacts with Hydrobon catalyst and catalyst for hydro-upgrading A successively and carries out hydrogenation reaction；Hydrotreatment reaction effluent enters hydro-upgrading reaction zone, successively with catalyst for hydro-upgrading B and contacting with Hydrobon catalyst, carries out hydrogenation reaction, and hydrofinishing effluent obtains product through air stripping.

In the inventive method, hydrotreatment reaction zone loads Hydrobon catalyst and catalyst for hydro-upgrading A from top to bottom, and the admission space ratio of Hydrobon catalyst and catalyst for hydro-upgrading A is 2～6:1～3, it is preferred to 4～6:1～2.

In the inventive method, hydro-upgrading reaction zone loads catalyst for hydro-upgrading B and Hydrobon catalyst from top to bottom, and the admission space of catalyst for hydro-upgrading B and Hydrobon catalyst is preferably 1:2～4 than for 1:1.5～5.

In the inventive method, the process conditions of hydrotreatment reaction zone are: reaction pressure 4.0～15.0MPa, it is preferred to 8.0～13.0MPa, and reaction temperature is 200～340 DEG C, it is preferred to 270～320 DEG C；Volume space velocity is 0.5～2.5h^-1, it is preferred to 0.4～1.0h^-1；Hydrogen to oil volume ratio is 80:1～800:1, it is preferred to 200:1～400:1.

In the inventive method, the process conditions of hydro-upgrading reaction zone are: reaction pressure 8.0～20.0MPa, it is preferred to 8.0～15.0MPa, and reaction temperature is 220～300 DEG C, it is preferred to 240～270 DEG C；Hydrogen to oil volume ratio is 80:1～500:1, it is preferred to 200:1～300:1；Volume space velocity is 0.1～1.0h^-1, it is preferred to 0.2～0.5h^-1。

In the inventive method, described wax material can be by vacuum distillate or through the decompression residuum of solvent deasphalting with or without furfural treatment, then through the waxy stone that benzol-kentone dewaxing obtains, described waxy stone can with or without clay finishing；Or furfural refining oil elder generation hydrotreatment, then the wax that benzol-kentone dewaxing obtains.

In the inventive method, hydrotreatment reaction zone is substantially carried out the reaction of hydrogenation and removing sulfur nitrogen oxygen and part aromatic hydrocarbons open loop saturated reaction.The active component of described Hydrobon catalyst is mainly transition metal and compound thereof, including Mo, W and Co, Ni, Fe and Pd of VIII, Pt etc. of group vib, it is preferable that high-nickel catalyst or palladium catalyst.With catalyst weight, the mass fraction of nickel respectively 15%～40%, it is preferable that 20%～30%, carrier Al₂O₃.Catalyst aperture is 3-15nm, and pore volume is 0.2-0.6L/g, and specific surface area is 100-400m²/g；Preferred catalyst aperture 4-8nm, pore volume is 0.2-0.4mL/g and specific surface area is 200-300m²/g。

Consider that the long-term hydrogenation activity of catalyst is had impact by the impurity such as the sulfur nitrogen in raw material, use the time for extending catalyst, it is possible to setting up auxiliary protection beds on major catalyst, it primarily serves protective effect.The hydrogenation protecting catalyst adopted is the deferrization protective agent that this area is conventional.Its amount is the 1/20～1/8 of major catalyst.

In the inventive method, hydrotreatment reaction zone uses the catalyst for hydro-upgrading A containing amorphous silica-alumina and modified Y zeolite.Described catalyst for hydro-upgrading A contains: the group VIII metal (in oxide) of 10wt%～35wt% amorphous silica-alumina, the modified Y zeolite of 2wt%～15wt%, the group VIB metal (in oxide) of 20wt%～50wt% and 8wt%～15wt%.The character of amorphous silica-alumina wherein used is as follows: silicon oxide-containing 20wt%～70wt%, specific surface is 350～600m²/ g, pore volume is 1.0～2.0mL/g, and infrared acidity is 0.20～0.40mmol/g, and the pore volume of bore dia 4～10nm accounts for the 85%～95% of total pore volume, > pore volume of 15nm accounts for less than the 5% of total pore volume；Preferred property is as follows: silicon oxide-containing 25wt%～40wt%, and specific surface is 500～630m²/ g, pore volume is 1.2～1.6mL/g.The character of modified Y zeolite wherein used is as follows: SiO₂/Al₂O₃Mol ratio is 40～60, and lattice constant is 2.420～2.450nm, and relative crystallinity is 85%～95%, infrared acidity 0.2～0.4mmol/g, and wherein the middle strong acid distribution of 300～500 DEG C is concentrated, and accounts for the 60～70% of total acid, and specific surface area is 500～1000m²/ g, pore volume 0.35～0.55mL/g, wherein the pore volume of the secondary mesopore of 4～15nm accounts for the 35%～55% of total pore volume.The specific surface area of catalyst for hydro-upgrading is 220～300m²/ g, pore volume is 0.3～0.5mL/g, and the pore volume of bore dia 3～10nm accounts for the 80%～95% of total pore volume, it is preferred to 85%～95%, and infrared acidity is at 0.2～0.4mmol/g.

In the inventive method, hydro-upgrading reaction zone uses the high-activity hydrogenation modifying catalyst containing amorphous silica-alumina and modified Y zeolite.Described catalyst for hydro-upgrading contains: the group VIII metal (in oxide) of 20wt%～60wt% amorphous silica-alumina, the modified Y zeolite of 3wt%～25wt%, the group VIB metal (in oxide) of 10wt%～30wt% and 4wt%～10wt%.The character of amorphous silica-alumina wherein used is as follows: silicon oxide-containing 10wt%～60wt%, specific surface is 400～650m²/ g, pore volume is 1.0～1.8mL/g, and infrared acidity is 0.34～0.50mmol/g, and the pore volume of bore dia 4～10nm accounts for the 85%～95% of total pore volume, > pore volume of 15nm accounts for less than the 5% of total pore volume；Preferred property is as follows: silicon oxide-containing 10wt%～35wt%, and specific surface is 530～650m²/ g, pore volume is 1.2～1.5mL/g.The character of modified Y zeolite wherein used is as follows: SiO₂/Al₂O₃Mol ratio is 40～60, and lattice constant is 2.425～2.440nm, and relative crystallinity is 80%～100%, infrared acidity 0.1～0.5mmol/g, and wherein the middle strong acid distribution of 250～550 DEG C is concentrated, and accounts for the 60～70% of total acid, and specific surface area is 600～900m²/ g, pore volume 0.3～0.6mL/g, wherein the pore volume of the secondary mesopore of 4～15nm accounts for the 40%～50% of total pore volume.Catalyst for hydro-upgrading can also contain the components such as aluminium oxide, zirconium oxide, titanium oxide.The specific surface area of catalyst for hydro-upgrading is 220～300m²/ g, pore volume is 0.3～0.6mL/g, and the pore volume of bore dia 3～10nm accounts for the 75%～95% of total pore volume, it is preferred to 85%～95%, and infrared acidity is at 0.3～0.5mmol/g.

In the inventive method, catalyst for hydro-upgrading A is compared with the composition of catalyst for hydro-upgrading B, group VIB metal in catalyst for hydro-upgrading B and group VIB total metal content 3～15 percents higher than the two total content in catalyst for hydro-upgrading A, amorphous silica-alumina in catalyst for hydro-upgrading B and the total content of modified Y zeolite 3～25 percents lower than the total content of the two in catalyst for hydro-upgrading A.

In the inventive method, the Hydrobon catalyst of hydrotreatment reaction zone and the Hydrobon catalyst composition of hydro-upgrading reaction zone can be identical or different.

In the inventive method, the Hydrobon catalyst active component of hydro-upgrading reaction zone is mainly transition metal and compound thereof, including Mo, W and Co, Ni, Fe and Pd of VIII, Pt etc. of group vib, preferred Mo, W component, content 10%～30%, it is preferable that 20%～30%, carrier Al₂O₃.Catalyst aperture is 3-15nm, and pore volume is 0.2-0.6L/g, and specific surface area is 100-400m²/g；Preferred catalyst aperture 4-8nm, pore volume is 0.35-0.5mL/g and specific surface area is 150-200m²/g。

nullCompared with prior art，Present invention process method has the advantage that in the inventive method，First pass through hydrofining reaction on top, hydrotreatment reaction zone and remove a large amount of sulfur nitrogen，Fractional saturation condensed-nuclei aromatics simultaneously，Due to hydrofining reaction heat release，Make hydrotreatment reaction zone temperature of lower of a relatively high，Not only it is subject to thermodynamic effects but also be subject to the reversible reaction of kinetic effect owing to hydrogenation saturated reaction is one，In the inventive method，Low by loading vector contg in bottom, hydrotreatment reaction zone、Hydrogenation component content height and hydrogenation activity are high，The catalyst for hydro-upgrading A that upgrading activity is low，Under the matching effect of catalyst for hydro-upgrading A Hydrogenation and open-loop performance，Ensure that condensed-nuclei aromatics hydrogenation saturated reaction forward carries out ring-opening reaction while carrying out，At utmost avoid the generation of the back reaction of condensed-nuclei aromatics hydrogenation saturated reaction，And catalyst for hydro-upgrading A open loop activity is low，Side chain cleavage reaction will not be there is，Make the aromatic hydrocarbons that the number of rings of the condensed-nuclei aromatics saturated generation belt length side chain of hydrogenation is relatively low，And sulfur nitrogen can be removed further，Ensure that wax product yield，Oil content is made not increase，Break simultaneously and hindered condensed-nuclei aromatics saturated sterically hindered further，Can react when more relaxing for hydro-upgrading reaction zone and create condition，Such hydro-upgrading reaction zone can be at lower temperatures，Carry out further aromatic hydrocarbons open loop and hydrogenation is just relatively simple to carry out.

Detailed description of the invention

The preparation process of the catalyst for hydro-upgrading of the present invention includes: after amorphous silica-alumina and modified Y zeolite mix homogeneously, add binding agent kneading, roll agglomerating after, extruded moulding on banded extruder and obtain carrier, then load hydrogenation active metals.

The preparation method of amorphous silica-alumina used, comprises the steps:

A, preparation sodium aluminate solution, sodium silicate solution；

B, sodium aluminate solution and sodium silicate solution stream are joined in plastic cans, ventilate simultaneously and pass into CO₂Gas, adjusts sodium aluminate solution, sodium silicate solution and CO₂Flow, controlling material pH value in plastic cans is 9～11, and controlling to neutralize reaction temperature is 20 ~ 50 DEG C, and the neutralization response time is 0.5～1.5 hour；

C, at the control temperature and pH value of step b, said mixture ventilate stablize 0.5～3.0 hour, it is preferred to 0.5～1.0 hour；

D, the solidliquid mixture of step c gained is filtered and washs；

E, step d drying and crushing is obtained amorphous silica-alumina.

In step a, the concentration of sodium aluminate solution is 25 ~ 60gAl₂O₃/ L, it is desirable to be 30～45gAl₂O₃/ L, the concentration of sodium silicate solution is 100～250gSiO₂/ L, it is desirable to be 100～150gSiO₂/L。

The serosity of step d gained filtered and uses 50 ~ 90 DEG C of deionized waters to be washed till neutrality, then drying 6 ~ 8 hours at 110 ~ 130 DEG C.

PH value in step b is generally constant is 9～11, it is desirable to be 9.5～10.5；The neutralization response time is generally 0.5～1.5 hour, it is desirable to be 45～60 minutes.

In step b, CO₂Concentration is 20v% ~ 50v%.Ventilation refers to pass into gas bottom reaction plastic cans, makes reaction system uniform, it is possible to pass into air or other is without CO₂Gas.

Amorphous silica-alumina is prepared with sodium aluminate, sodium silicate and carbon dioxide for raw material.The method is particularly suitable for adopting the producer of sintering process explained hereafter aluminium oxide, with its intermediate products sodium aluminate solution and by-product CO₂Gas is raw material production amorphous silica-alumina, produced Na₂CO₃Mother solution can circulate to sintering process to provide part Na₂CO₃, form closed cycle, and do not produce contaminated wastewater.

Modified Y zeolite is passed through pH value NH between 1 ~ 3 by NaY₄ ⁺Exchange, hydrothermal treatment consists and what acid treatment was prepared from.Concrete preparation process is as follows:

NaY zeolite passes through a NH₄NO₃After exchange, then again with oxalic acid and NH₄NO₃Mixed liquor, carries out second time NH at pH value between 1 ~ 3₄ ⁺Exchange, under the condition of 0.080 ~ 0.098MPa and 500 ~ 550 DEG C, then carry out first time hydrothermal treatment consists, after first time hydrothermal treatment consists, carry out NH again₄NO₃Exchange, carries out second time hydrothermal treatment consists, and second time hydrothermal conditions is 0.1 ~ 0.2MPa and 500 ~ 700 DEG C.Finally use HNO₃Carry out acid treatment, obtain modified Y zeolite.

The carrying method of catalyst for hydro-upgrading active metal, it is possible to adopt the routine techniques such as kneading method, infusion process to prepare, it is desirable to adopt first extruded moulding then the mode of impregnating metal component.After the preparation of catalyst of the present invention adopts modified Y zeolite to mix homogeneously with contained amorphous silica-alumina dry glue powder, add the appropriate binding agent prepared by SB aluminium oxide and nitric acid peptization, kneading or be rolled into paste, extruded moulding, it is generally the cylindrical bars of diameter 3 ~ 8 millimeters.Carrier dried 4 ~ 14 hours through 100 ~ 130 DEG C, 500 ~ 600 DEG C of roastings 3 ~ 10 hours.After activation, adopt the saturated or excessive impregnation liquid dipping impregnation liquid containing hydrogenation metal, then carry out 100 ~ 130 DEG C dry 4 ~ 14 hours, roasting 3 ~ 10 hours at 450 ~ 550 DEG C and make catalyst.

Example 1 below is amorphous silica-alumina preparation process involved by catalyst of the present invention, and example 2 is hydro-upgrading catalyst for hydro-upgrading A preparation process, and example 3 is hydro-upgrading catalyst for hydro-upgrading B preparation process.

Embodiment 1

It is 200gAl that 700 solid sodium aluminates are configured to concentration₂O₃The dense sodium aluminate solution of/L, then to be diluted to concentration be 35gAl₂O₃/ L sodium aluminate working solution (a), takes containing SiO₂The sodium silicate solution of 28wt%, then to be diluted to concentration be 150gSiO₂/ L sodium silicate working solution 2L(b).Take the steel plastic cans of a 30L, open the container valve having (a) and (b) respectively simultaneously, ventilate simultaneously and pass into the CO that concentration is 45v%₂Gas, the flow setting (a) and (b) makes the response time at 1 hour, and adjusts rapidly CO₂Flow, make the pH of system be maintained at about 10.0, reaction temperature 30 DEG C, after (a) and (b) have reacted, stop passing into CO₂, then ventilating and stablize 40 minutes, serosity filters and uses 85 DEG C of deionized waters to be washed till neutrality.Dry 8 hours at 120 DEG C, pulverize and sieve to obtain amorphous silica-alumina GL.This amorphous silica-alumina silicon oxide-containing 30wt%, after activation, specific surface is 560m²/ g, pore volume is 1.41ml/g, and infrared acidity is 0.42mmol/g, and the pore volume of bore dia 4～10nm accounts for the 90% of total pore volume, > 15nm pore volume accounts for the 3% of total pore volume.

Embodiment 2

Take 80g sial GL, 30g modified Y zeolite (SiO₂/Al₂O₃Be 40, lattice constant be 2.432nm, infrared acidity 0.19mmol/g specific surface 866m²/ g, pore volume 0.52ml/g) with the 250g binding agent being made up of nitric acid and SB alumina peptization, kneading, roll, make can the paste of extrusion, extruded moulding.110 DEG C dry 6 hours, 550 DEG C of roastings 4 hours, prepares carrier A.Again with 200ml Mo-Mi co-impregnated solution excessive dipping 80gA2 hour, 110 DEG C dry 6 hours, 500 DEG C of roastings 4 hours, prepares catalyst for hydro-upgrading A.Catalyst for hydro-upgrading physical property is in Table 1.

Embodiment 3

Take 100g sial GL, 45g modified Y zeolite (SiO₂/Al₂O₃Be 40, lattice constant be 2.432nm, infrared acidity 0.19mmol/g specific surface 866m²/ g, pore volume 0.52ml/g) with the 310g binding agent being made up of nitric acid and SB alumina peptization, kneading, roll, make can the paste of extrusion, extruded moulding.110 DEG C dry 6 hours, 550 DEG C of roastings 4 hours, prepares carrier B.Again with 200ml Mo-Mi co-impregnated solution excessive dipping 80gA2 hour, 110 DEG C dry 6 hours, 500 DEG C of roastings 4 hours, prepares catalyst for hydro-upgrading B.Catalyst for hydro-upgrading physical property is in Table 1.

Table 1 catalyst for hydro-upgrading physico-chemical property

Catalyst is numbered	Catalyst for hydro-upgrading A	Catalyst for hydro-upgrading B
			MoO₃, wt%	28.5	19.0
NiO, wt%	10.0	6.0
			Specific surface area, m²/g	241	256
Pore volume, ml/g	0.42	0.46
			The pore volume of bore dia 3～10nm accounts for total pore volume, %	91.0	91.4
Infrared total acidity, mmol/g	0.285	0.361

In the embodiment of the present invention, described Hydrobon catalyst selects commodity industrial paraffin hydrogenation catalyst FV-10, FV-20.

Raw material 1: No. 68 wax materials through furfural treatment: fusing point 69.5 DEG C, Saybolt color number+6, oil content 0.5%, containing toluene amount 20mg/kg, C₆-C₈Ketone 12mg/kg, smells taste 2.0.

Raw material 2:80 crystallite wax material: fusing point 80.9 DEG C, color 2.0(GB6540), oil content 1.5%, containing toluene amount 15mg/kg, C₆-C₈Ketone 14mg/kg, smells taste 2.0.

Embodiment 4

In the present embodiment, adopting raw material 1 to react, in hydrotreating reactor, Hydrobon catalyst adopts FV-10 catalyst, and in hydrotreating reactor, FV-10 catalyst and catalyst for hydro-upgrading A admission space from top to bottom are 5:1.In hydro-upgrading reactor, catalyst for hydro-upgrading B and FV-10 catalyst admission space from top to bottom are 1:2.The operating condition of hydrotreatment reaction zone is pressure 13.0MPa, temperature 270 DEG C, and the operating condition of hydro-upgrading reaction zone is, pressure 13.0MPa, temperature 240 DEG C, raw material 1 inlet amount 200ml/h, hydrogen flowing quantity 30L/h.Run 20 h before harvest products, logical N₂Air stripping at 200 DEG C, obtains product.

Embodiment 5

In the present embodiment, difference from Example 4 is: adopting raw material 2, the temperature of hydrotreatment reaction zone 300 DEG C, the temperature of hydro-upgrading reaction zone 250 DEG C, raw material 2 inlet amount 100ml/h, hydrogen flowing quantity are 50L/h.All the other are identical with embodiment 4.

Embodiment 3

Identical with embodiment 5, difference is, the temperature of hydrotreatment reaction zone is 310 DEG C, wherein, the admission space of Hydrobon catalyst FV-20 and catalyst for hydro-upgrading A is than for 4:1, and in hydro-upgrading reaction zone, the admission space of catalyst for hydro-upgrading B and FV-10 catalyst is than for 1:2.

Comparative example 1

Substantially the same manner as Example 4, difference is, catalyst for hydro-upgrading A is not loaded in hydrotreatment reaction zone.

Comparative example 2

Substantially the same manner as Example 5, difference is, catalyst for hydro-upgrading A is not loaded in hydrotreatment reaction zone, and catalyst for hydro-upgrading B is not loaded in hydro-upgrading reaction zone.

The product property of each embodiment of table 2 and comparative example

	Embodiment 4	Embodiment 5	Embodiment 6	Comparative example 1	Comparative example 2
						Saybolt color, number	+30	+30	+30	+30	+27
Light stability	2	-	-	3	-
						Bromine taste	0.5	1.0	1.0	1.0	1.5
Toluene	0	0	0	0	0
						C₆-C₈Ketone mg/kg	0.4	1.0	1.0	2.0	3.0
Oil content, %	0.50	1.51	1.50	0.50	1.51

Claims

1. a high melting-point wax hydrogenation method, including following content: wax material enters hydrotreatment reaction zone, contacts with Hydrobon catalyst and catalyst for hydro-upgrading A successively and carries out hydrogenation reaction；Hydrotreatment reaction effluent enters hydro-upgrading reaction zone, successively with catalyst for hydro-upgrading B and contacting with Hydrobon catalyst, carry out hydrogenation reaction, hydrofinishing effluent obtains product through air stripping, contains in described catalyst for hydro-upgrading A: 10wt%～35wt% amorphous silica-alumina, the modified Y zeolite of 2wt%～15wt%, the group VIB metal in oxide 20wt%～50wt% and the group VIII metal in oxide 8wt%～15wt%；Described catalyst for hydro-upgrading B contains the amorphous silica-alumina of 20wt%～60wt%, the modified Y zeolite of 5wt%～25wt%, in the group VIB metal of oxide 10wt%～30wt% with in the group VIII metal of oxide 4wt%～10wt%, catalyst for hydro-upgrading A is compared with the composition of catalyst for hydro-upgrading B, in catalyst for hydro-upgrading B in oxide group VIB metal and group VIII metal total content than in catalyst for hydro-upgrading A in high 3～15 percents of the two total content of oxide, amorphous silica-alumina in catalyst for hydro-upgrading B and the total content of modified Y zeolite 3～25 percents lower than the total content of the two in catalyst for hydro-upgrading A.

2. in accordance with the method for claim 1, it is characterised in that: hydrotreatment reaction zone loads Hydrobon catalyst and catalyst for hydro-upgrading A from top to bottom, and the admission space ratio of Hydrobon catalyst and catalyst for hydro-upgrading A is 2～6:1～3.

3. in accordance with the method for claim 2, it is characterised in that: the admission space ratio of Hydrobon catalyst and catalyst for hydro-upgrading A is 4～6:1～2.

4. in accordance with the method for claim 1, it is characterised in that: hydro-upgrading reaction zone loads catalyst for hydro-upgrading B and Hydrobon catalyst from top to bottom, and the admission space of catalyst for hydro-upgrading B and Hydrobon catalyst is than for 1:1.5～5.

5. the method described in claim 1 or 4, it is characterised in that: hydro-upgrading reaction zone loads catalyst for hydro-upgrading B and Hydrobon catalyst from top to bottom, and the admission space of catalyst for hydro-upgrading B and Hydrobon catalyst is than for 1:2～4.

6. in accordance with the method for claim 1, it is characterised in that: the process conditions of hydrotreatment reaction zone are: reaction pressure 4.0～15.0MPa, reaction temperature 200～340 DEG C, volume space velocity 0.5～2.5h^-1, hydrogen to oil volume ratio is 80:1～800:1.

7. the method described in claim 1 or 6, it is characterised in that: the process conditions of hydrotreatment reaction zone are: reaction pressure 8.0～13.0MPa, reaction temperature 270～320 DEG C, volume space velocity 0.4～1.0h^-1, hydrogen to oil volume ratio is 200:1～400:1.

8. in accordance with the method for claim 1, it is characterised in that: the operating condition of hydro-upgrading reaction zone is: reaction pressure is 8.0～20.0MPa, and reaction temperature is 220～300 DEG C, and hydrogen to oil volume ratio is 80:1～500:1, and volume space velocity is 0.1～1.0h^-1。

9. the method described in claim 1 or 8, it is characterised in that: the operating condition of hydro-upgrading reaction zone is: reaction pressure is 8.0～15.0MPa, and reaction temperature is 240～270 DEG C；Hydrogen to oil volume ratio is 200:1～300:1；Volume space velocity is 0.2～0.5h^-1。

10. in accordance with the method for claim 1, it is characterised in that: in described catalyst for hydro-upgrading A and catalyst for hydro-upgrading B, the character of amorphous silica-alumina is as follows: silicon oxide-containing 10wt%～60wt%, and specific surface is 400～650m²/ g, pore volume is 1.0～1.8mL/g, and infrared acidity is 0.34～0.50mmol/g, and the pore volume of bore dia 4～10nm accounts for the 85%～95% of total pore volume, > pore volume of 15nm accounts for less than the 5% of total pore volume.

11. in accordance with the method for claim 1, it is characterised in that: the modified Y zeolite in described catalyst for hydro-upgrading A and catalyst for hydro-upgrading B has the property that SiO₂/Al₂O₃Mol ratio is 40～60, and lattice constant is 2.425～2.440nm, and relative crystallinity is 80%～100%, infrared acidity 0.1～0.5mmol/g, and wherein the middle strong acid distribution of 250～550 DEG C is concentrated, and accounts for the 60～70% of total acid, and specific surface area is 600～900m²/ g, pore volume 0.3～0.6mL/g, wherein the pore volume of the secondary mesopore of 4～15nm accounts for the 40%～50% of total pore volume.

12. in accordance with the method for claim 1, it is characterised in that: the Hydrobon catalyst of hydrotreatment reaction zone and the Hydrobon catalyst composition of hydro-upgrading reaction zone are identical or different.

13. in accordance with the method for claim 1, it is characterized in that: described wax material be by vacuum distillate or through the decompression residuum of solvent deasphalting with or without furfural treatment, then through the waxy stone that benzol-kentone dewaxing obtains, described waxy stone is with or without clay finishing；Or furfural refining oil elder generation hydrotreatment, then the wax that benzol-kentone dewaxing obtains.