CN106669815A - Method for in-situ one-step synthesis of two molecular sieve catalysts - Google Patents

Abstract

The invention discloses a method for in-situ one-step synthesis of two molecular sieve catalysts. The method comprises the following steps: (1), filling a catalyst precursor containing amorphous silica-alumina and active metal components into upper and lower bed layers of a quench type two-section adiabatic fixed-bed reactor; (2), introducing aqueous solution containing diamines compounds, for contact reaction with the catalyst precursor in the upper and lower bed layers; (3), ensuring that materials in the reactor is subjected to the treatment of oxygen-containing gas, introducing a ammonium nitrate solution into the materials to perform contact reaction, introducing nitrogen into the materials to treat the materials, finally introducing gas containing hydrogen to perform activating treatment, and ensuring that a ZSM-5 molecular sieve catalyst is formed on the surface of the upper bed layer and a ZSM-22 molecular sieve catalyst is formed on the surface of the lower bed layer. The method has the advantages that molecular sieves formed on the surfaces of the catalysts are uniformly distributed, the utilization of the molecular sieves is improved, and the method is beneficial to the diffusion of products, improves the reaction selectivity and activity, and has the characteristics of high lubricant base oil yield, high viscosity index and low pour point particularly when raw materials with high wax contents are treated. Meanwhile the production cost of catalysts is greatly reduced, the generation of wastewater which is difficult to treat during the synthesis of traditional molecular sieves is avoided, and the method is beneficial to environmental protection.

Description

A kind of method of two kinds of molecular sieve catalysts of in-situ one-step synthesis

Technical field

The present invention relates to a kind of method of two kinds of molecular sieve catalysts of in-situ one-step synthesis.

Background technology

Dewaxing reaction is that the hydrocarbon is particularly straight chain and the alkane of slight branched chain easily solidifies by processing the method that petroleum distillate removes specific hydrocarbon（Wax）, dewaxing can be realized by solvent extraction and crystallization.In recent years, the comparison for converting with regard to selective catalysis and removing the technique study of wax is more, and in the case of production lube base oil, catalytic dewaxing is generally with undesirable viscosity index (VI)（VI）Reduction.Catalytic dewaxing is generally worked by two kinds of mechanism, isomerization and cracking, and the loss of VI is generally related to cracking mechanism.Therefore, develop high isomerization selectivity but the dewaxing catalyst system of low Cracking Selectivity is increasingly paid close attention to by people.

It is many with regard to the report of isomerization dewaxing catalyst at present, such as US5990371, US5833837, US5817907, US5149421, US5135638, US5110445, US4919788, US4419420, US4601993 and US4518485 etc. all relate to Isodewaxing Technology, wherein the acidic components for using mainly have modenite, SAPO-11, SAPO-31, SAPO-41, ZSM-23, SSZ-32, TON type molecular sieve etc..US4222855 discloses boiling point in about 450 to 1050 ℉（232 to 566 DEG C）In the range of waxy hydrocarbon fraction, contact with the catalyst comprising the aluminosilicate zeolites and hydrogenation metal for being selected from ZSM-23 and ZSM-35, prepare and there is high VI, the lubricating oil of low pour point, the VI values of the dewaxed oil that the method is obtained are much larger than the dewaxed oil obtained with ZSM-5 catalyst.US5075269 is disclosed using acid zeolite ZSM-48, the ZSM-48 synthesized as structure directing agent especially with organic linear diquaternary amine compound as catalyst, can catalytic dewaxing wax hydrocarbon ils preparing high-viscosity index lubricating oil raw material.It is reported that the dewaxed oil is also with higher than the VI by the dewaxed oil obtained with ZSM-5.U.S. Patent application 2007/0029229 discloses a kind of process for dewaxing, and the method includes making hydrocarbon feed contact with the catalyst of the combination comprising following material under dewaxing conditions：Zeolite with MTT framework structure types, such as ZSM-23 and the zeolite with GON framework structure types, a kind of with one-dimensional passage 12 Yuans ring/8 Yuan ring zeolites, such as GUS-1.It is reported that work as to be used to make to be more than 1000 ℉ with major part boiling point（538℃）Hydrocarbon oil crude material dewax when, specific combination of zeolites significantly increases heavy wax（Long-chain normal alkane）Conversion ratio, thus reduce product cloud point.U.S. Patent application 2007/0029230 discloses a kind of process for dewaxing, and the method includes making hydrocarbon feed contact with the catalyst of the combination comprising following material under dewaxing conditions：Zeolite with MTT framework structure types, such as ZSM-23, and the zeolite with MTW framework structure types, such as ZSM-12, the grain size number of the MTT and MTW zeolites is less than 0.1 micron.When for making hydrocarbonaceous charging dewax, it was reported that compared with the viscosity index (VI) of waxy feed, the MTT/MTW combination of zeolites improves the viscosity index (VI) of dewaxed product.

The purpose of isomerization dewaxing is exactly to make high melting-point wax be converted into the relatively low isoparaffin of fusing point, but it is also many that the high alkane viscosity index (VI) of isomerisation degree declines, so must just control the isomerisation degree of wax molecule, this just proposes strict requirements to the Acidity and pore structure and hydrogenation component of isomerization dewaxing catalyst acidic components.In general acidic components will have moderate strength, more and with space restriction effect the pore structure of acid amount, and active metal component has quick hydrogenation/dehydrogenation activity, prevents further isomery or even the cracking of tertiary carbonium ion.Although the pore structure that above-mentioned these materials have the acid centre of moderate strength and match with wax molecule, there is obvious space to limit to highly-branched chain isomerous body, can to a certain extent make paraffin hydrocarbon that isomerization reaction occurs, but due in catalyst preparation process, it is capped can most acid centre, the acidity of catalyst for obtaining is weaker, and activity and selectivity is relatively low.And for lube cut, due to wherein containing very complicated component, it is not that identical molecule participates in reaction, so for the molecular sieve with homogeneous structural just occurs some adaptive problems, the catalysis material of good match is capable of to a kind of molecule, for other component may be less desirable.Therefore, this is desirable to a catalyst simultaneously with shape-selective cracking and isomerization multi-functional, and good effect is not reached if using single molecular sieve.

ZSM-5 molecular sieve belongs to MFI topological structures, due to the straight channel with 0.54nm × 0.56nm sizes and the pore structure of the three dimensional intersection in the sinusoidal duct of 0.51 nm × 0.55nm sizes, with more preferable cracking activity and lower level of deactivation；ZSM-22 molecular sieves belong to TON topological structures, one-dimensional tunnel structure with ten-ring, port size 0.44nm × 0.55nm, due to the duct feature of the molecule itself, the molecular sieve analog shows very high catalysis activity and selectivity in alkene and alkane isomerization reaction, with the incomparable superiority of other catalyst, there is good application prospect.

There are many reports with regard to the synthetic method of ZSM-22 molecular sieves and ZSM-5 molecular sieve, typically all under alkaline environment, organic amine is structure directing agent, at a certain temperature crystallization certain hour.Can produce in this building-up process substantial amounts of containing the industrial wastewater such as organic amine and alkali, it is difficult to carry out harmless treatment, not only greatly improve molecular sieve production cost, and cause serious environmental pollution so as to using greatly being limited.

The content of the invention

For the deficiencies in the prior art, the present invention provides a kind of method of two kinds of molecular sieve catalysts of in-situ one-step synthesis, and the method forms two distinct types of molecular sieve by the crystallization temperature of upper and lower two beds of control reactor in catalyst precursor surface.Both molecular sieves have different pore passage structure and acidic character, and embody good cooperative effect.The method is evenly distributed in the molecular sieve that catalyst surface is formed, improve the utilization rate of molecular sieve, be conducive to the diffusion of product, improve reaction selectivity and activity, considerably reduce Catalyst Production cost simultaneously, the generation of the intractable waste water of conventional synthesis molecular sieve process is avoided, is conducive to environmental protection.

The method of two kinds of molecular sieve catalysts of in-situ one-step synthesis of the present invention, including following content：

（1）Catalyst precarsor containing amorphous silica-alumina and active metal component is loaded into the upper and lower bed of two sections of insulation fix bed reactors of cold shock formula；

（2）The aqueous solution containing diamine compounds is passed through, the catalyst precarsor haptoreaction with upper and lower two beds：Wherein upper bed layer temperature is 195 ~ 215 DEG C, and lower bed layer temperature is 145 ~ 165 DEG C；

（3）Material in reactor is again through oxygen-containing gas process, then pass to aqueous ammonium nitrate solution haptoreaction, then pass to nitrogen to be processed, the gas activation for being finally passed through hydrogen is processed, the catalyst of the surface for ZSM-5 molecular sieve of upper bed layer is obtained, the surface of lower bed layer is the catalyst of ZSM-22 molecular sieves.

In the inventive method, step（1）Described catalyst precarsor has following property：The SiO of described amorphous silicon aluminium₂And Al₂O₃Mol ratio be 5 ~ 200, preferably 10 ~ 100；Described active metal component is platinum or/and palladium, preferably platinum, and on the basis of total catalyst weight, active component content is calculated as 0.1% ~ 10%, preferably 0.1% ~ 2%, more preferably 0.2% ~ 1.0% with metal.Described preparation method can be prepared according to prior art, and general process is as follows：Aluminum hydroxide solid elastomer powder, white carbon, sesbania powder are sufficiently mixed, peptizing agent is subsequently adding（Sodium hydroxide solution）, kneading is plastic paste, extruded moulding, drying, calcination process, then supported active metals component, drying and calcination process, obtains catalyst precarsor.Concrete preparation condition can determine according to this area Conventional wisdom.

In the inventive method, step（1）The characteristics of described reactor is the two sections of insulation fix bed reactors of cold shock formula for having cold shock gas using centre, and catalyst precarsor is loaded into respectively in upper and lower two reactor beds.The reaction temperature of upper and lower two beds is controlled by cold shock gas.

In the inventive method, step（2）It is C that the diamine compounds are carbon numbers₅~C₈Diamines, preferably one or more in hexamethylene diamine, octamethylenediamine and heptamethylene diamine.Described diamine compounds concentration in aqueous is 0.01 ~ 2mol/L, preferably 0.1 ~ 1 mol/L.

In the inventive method, step（2）The described inlet amount containing the diamine compounds aqueous solution is 0.1 ~ 10, preferably 0.5 ~ 5 with catalyst volume ratio；Described haptoreaction condition is：Reaction pressure is 0.2 ~ 10MPa, preferably 0.5 ~ 5MPa；The bed reaction temperature of two of which reactor is different, and upper bed layer reaction temperature is 195 ~ 215 DEG C, and preferably 200 ~ 210 DEG C, lower bed layer reaction temperature is 145 ~ 165 DEG C, preferably 150 ~ 160 DEG C；Reaction time is 12 ~ 100 hours, preferably 24 ~ 72 hours.

In the inventive method, step（3）The described oxygen-containing gas treatment conditions that are passed through are：Treatment temperature is 400 ~ 600 DEG C, gas agent volume ratio（Into the volume and the admission space ratio of catalyst of gas）100 ~ 1000, process time is 4 ~ 12 hours；Wherein described oxygen-containing gas is the one kind in the mixture of air, oxygen and nitrogen or the mixture of oxygen and inert gas, and oxygen volume fraction in the gas phase is 5% ~ 50%.

In the inventive method, step（3）The inlet amount of the aqueous solution containing ammonium nitrate is 0.1 with the volume ratio of catalyst:1~10:1, preferably 1:1~5:1, the wherein mass percent concentration of aqueous ammonium nitrate solution is 16% ~ 50%；Step（3）Described haptoreaction condition is：Reaction pressure is 0.2 ~ 10MPa, and preferably 0.5 ~ 5MPa, reaction temperature is that preferably 20 ~ 100 DEG C, the reaction time is 1 ~ 24 hour, preferably 2 ~ 12 hours less than the boiling temperature of water at this pressure.

In the inventive method, step（3）The described nitrogen treatment condition that is passed through is：100 ~ 300 DEG C for the treatment of temperature, gas agent volume ratio（Into the volume and the admission space ratio of catalyst of gas）100 ~ 1000, the time is 4 ~ 12 hours.

In the inventive method, step（3）The hydrogen gas can be pure hydrogen or the hydrogen containing inert gas, and the hydrogen volume degree wherein in hydrogen-containing gas is 5% ~ 100%, preferably 50% ~ 100%；Described activation process condition is：Pressure is 0.2 ~ 10MPa, and preferably 0.5 ~ 5MPa, temperature is 200 DEG C ~ 600 DEG C, and preferably 250 DEG C ~ 500 DEG C, the time is 0.5 ~ 24 hour, preferably 1 ~ 12 hour, more preferably 2 ~ 8 hours.

In step in the inventive method（3）Afterwards, reaction mass is passed directly into in reactor, carries out paraffin hydrocarbon selective isomerization reaction.

Two kinds of molecular sieve catalysts of the in-situ one-step synthesis that the inventive method is obtained are applied to paraffin hydrocarbon and select type isomerization reaction, and general process conditions are as follows：0.5 ~ 4.0h of volume space velocity^-1, reaction temperature is 200 ~ 400 DEG C, and reaction pressure is 2 ~ 20MPa, and hydrogen hydrocarbon mol ratio is 2 ~ 10；It is the technical process that long straight-chain alkane is converted into branched paraffin that wherein described paraffin hydrocarbon selects type isomerization reaction.Feedstock oil wherein used in the reaction of paraffin hydrocarbon selective isomerization is waxy feeds oil, generally comprise diesel oil, AGO, VGO, white oil, hydrocracking tail oil and lube cut etc., it is particularly suited for the higher feedstock oil of wax content, generally more than 50%, preferred wax content is between 50% ~ 80% for wax content.

The inventive method is by preparing catalyst precarsor（Mainly amorphous silicon aluminium surface）Catalyst precarsor is contacted with the organic compound aqueous solution, under a certain pressure, by the crystallization temperature for controlling upper and lower two beds, formed on the surface of reactor overlying catalyst precursor and there is the ZSM-5 molecular sieve for intersecting duct, formed on the surface of reactor lower catalyst agent precursor and be suitable to selective isomerization reaction ZSM-22 molecular sieve catalysts.Due to the pore passage structure and the difference of acidity of both molecular sieves, and embody good cooperative effect.During the course of the reaction, high wax stock first will contact with the catalysis of upper strata ZSM-5 molecular sieve, first divide cracking reaction by partly long direct-connected alkane generating unit, then be contacted with the ZSM-22 molecular sieve catalysts of reactor lower floor shape selectivity, carry out isomerization reaction.For lube oil hydrotreating process, particularly when high wax stock is processed, the characteristics of not only there is high lube base oil high income, viscosity index (VI) and low pour point with incomparable superiority.And the method can also improve the utilization rate of molecular sieve, catalyst can be considerably reduced into producing cost, it is to avoid the generation of the intractable waste water of conventional synthesis molecular sieve processes, be conducive to environmental protection.

Description of the drawings

Fig. 1 is the schematic diagram of two sections of insulation fix bed reactors of the present invention.

Specific embodiment

The technology of the present invention is described further below by embodiment, but should not be construed as being limited to this scope.Institute is shown in Table 1 using raw material oil nature.

Embodiment 1

（1）By 1200 grams of white carbons, 70 grams（Butt 76%）Aluminium hydroxide（The SB of German Condean companies production）It is sufficiently mixed with 40 grams of sesbania powders, it is subsequently adding the sodium hydroxide solution that 600ml concentration is 0.1M, abundant kneading, make paste plastic, forming diameter is the cylindrical bars of 1.5mm on banded extruder, the cylindrical bars are dried 16 hours at 100 DEG C, and then 550 DEG C of roastings obtain catalyst carrier in 4 hours in air atmosphere.With containing H₂PtCl₆Solution saturation impregnates said catalyst carrier, then 100 DEG C of dryings 8 hours again, and 500 DEG C of roastings 3 hours, are obtained the catalyst precarsor containing 0.5wt%Pt in air atmosphere.SiO in the catalyst₂And Al₂O₃Mol ratio be 38.100ml catalyst is taken, there are two sections of insulation fix bed reactors of cold shock formula of cold shock gas with centre is packed into respectively after the dilution of 100ml quartz sands（Upper and lower two beds）In carry out catalytically active assessment.

（2）Pressure be 2MPa, reaction temperature（205 DEG C of upper bed layer, 158 DEG C of lower bed layer）, in treatment fluid hexamethylene diamine concentration be 0.2 Mol/L, feed volume air speed（The volume for feeding per hour and the ratio of catalyst）2.0h^-1, process time 36 hours.Then stop into treatment fluid, with gas agent volume ratio（Into the volume and the admission space ratio of catalyst of gas）800 speed is passed through air, improves temperature to 550 DEG C, and the retention time is to start Temperature fall after 6 hours, obtains catalyst sample.

（3）When being reduced to 60 DEG C for temperature, start to be passed through the aqueous solution containing ammonium nitrate toward beds under normal pressure, feed volume air speed is 2.0h^-1, water inlet is stopped after being kept for 4 hours, with gas agent volume ratio（Into the volume and the admission space ratio of catalyst of gas）500 speed is passed through nitrogen, improves temperature to 200 DEG C, and the retention time is to stop within 4 hours being passed through nitrogen, and catalyst sample, numbering C-1 is obtained.

（4）In pressure 1MPa, with gas agent volume ratio（Into the volume and the admission space ratio of catalyst of gas）800 speed is passed through pure hydrogen, improves temperature to 350 DEG C, and the retention time carried out activation of catalyst for 4 hours.

（5）In pressure 5MPa, reaction temperature（245 DEG C of upper bed layer, 350 DEG C of lower bed layer）Under conditions of, hydrogen hydrocarbon mol ratio is 4, with volume space velocity as 6.0h^-1Into raw material shown in table 1, evaluating catalyst is carried out, negate and answer the product of 4 hours to be analyzed, evaluation result is shown in Table 2.

Embodiment 2

With embodiment 1, difference is step（2）Octamethylenediamine replaces hexamethylene diamine in treatment fluid, and the crystallization temperature of the upper and lower bed of reactor is 195 DEG C and 150 DEG C, and volume space velocity is 4.0 h^-1, process time 28 hours, air-treatment temperature is 580 DEG C, and the time is 4 hours, and catalyst sample, numbering C-2 is obtained.Evaluation result is shown in Table 2.

Embodiment 3

With embodiment 1, difference is step（2）The concentration of middle hexamethylene diamine is 0.6 Mol/L, and the crystallization temperature of the upper and lower bed of reactor is respectively 210 DEG C and 162 DEG C, and volume space velocity is 4.0 h^-1, process time 28 hours, prepared catalyst sample, numbering C-3.Evaluation result is shown in Table 2.

Embodiment 4

With embodiment 1, difference is step（2）The concentration of middle hexamethylene diamine is 0.6 Mol/L, and the crystallization temperature of the upper and lower bed of reactor is respectively 200 DEG C and 155 DEG C, and volume space velocity is 4.0 h^-1, process time 35 hours, prepared catalyst sample, numbering C-4.Evaluation result is shown in Table 2.

Embodiment 5

With embodiment 1, difference is step（3）In containing ammonium nitrate the aqueous solution feed volume air speed be 1.0h^-1, flooding time 8 hours, temperature is 25 DEG C, and nitrogen gas agent volume ratio is 300,260 DEG C of temperature, and the time is 6 hours, and catalyst sample, numbering C-5 is obtained.Evaluation result is shown in Table 2.

Embodiment 6

With embodiment 1, difference is step（3）Pressure be 0.5MPa, reduction temperature is 320 DEG C, and gas is the mixture of hydrogen and nitrogen（Wherein hydrogen volume degree is 60%）, gas agent volume ratio is 600, and the recovery time is 2 hours, and catalyst sample, numbering C-6 is obtained.Evaluation result is shown in Table 2.

Comparative example 1

（1）By 1200 grams of white carbons, 70 grams（Butt 76%）Aluminium hydroxide（The SB of German Condean companies production）It is sufficiently mixed with 40 grams of sesbania powders, it is subsequently adding the sodium hydroxide solution that 700ml concentration is 0.1M, abundant kneading, make paste plastic, forming diameter is the cylindrical bars of 1.5mm on banded extruder, the cylindrical bars are dried 16 hours at 100 DEG C, and then 550 DEG C of roastings obtain catalyst carrier in 4 hours in air atmosphere.With containing H₂PtCl₆Solution saturation impregnates said catalyst carrier, then 100 DEG C of dryings 8 hours again, and 500 DEG C of roastings 3 hours, are obtained the catalyst containing 0.5wt%Pt in air atmosphere.Numbering is E-1.SiO in the catalyst₂And Al₂O₃Mol ratio be 38.100ml catalyst is taken, there are two sections of insulation fix bed reactors of cold shock formula of cold shock gas with centre is packed into respectively after the dilution of 100ml quartz sands（Upper and lower two beds）In carry out catalytically active assessment.With embodiment 1, evaluation result is shown in Table 2 to appreciation condition.

Comparative example 2

（1）Prepare E-2a catalyst

By 100 grams（Butt 76%）Aluminium hydroxide（The SB of German Condean companies production）, 20 grams of ZSM-5 molecular sieves and 6 grams of sesbania powders are sufficiently mixed, it is subsequently adding the salpeter solution that 70ml concentration is 0.2M, abundant kneading, make paste plastic, the cylindrical bars of a diameter of 1.5mm are extruded on banded extruder, cylindrical bars are dried 16 hours at 100 DEG C, and then 550 DEG C of roastings obtain catalyst carrier in 4 hours in air atmosphere.With containing H₂PtCl₆Solution saturation impregnates said catalyst carrier, then 100 DEG C of dryings 8 hours, 500 DEG C of roasting 3h in air atmosphere again, and the catalyst containing 0.5wt%Pt, sample number into spectrum E-2a is obtained.

（2）Prepare E-2b catalyst

By 100 grams（Butt 76%）Aluminium hydroxide（The SB of German Condean companies production）, 40 grams of ZSM-22 molecular sieves and 6 grams of sesbania powders are sufficiently mixed, it is subsequently adding the salpeter solution that 70ml concentration is 0.2M, abundant kneading, make paste plastic, the cylindrical bars of a diameter of 1.5mm are extruded on banded extruder, cylindrical bars are dried 16 hours at 100 DEG C, and then 550 DEG C of roastings obtain catalyst carrier in 4 hours in air atmosphere.With containing H₂PtCl₆Solution saturation impregnates said catalyst carrier, then 100 DEG C of dryings 8 hours, 500 DEG C of roasting 3h in air atmosphere again, and the catalyst containing 0.5wt%Pt, sample number into spectrum E-2b is obtained.

（3）E-2a and E-2b catalyst 100ml are taken respectively, there are two sections of insulation fix bed reactors of cold shock formula of cold shock gas with centre is packed into respectively after the dilution of 100ml quartz sands（Upper and lower two beds）In carry out catalytically active assessment.With embodiment 1, evaluation result is shown in Table 2 to appreciation condition.

Comparative example 3

With embodiment 1, difference is using one section of fixed bed reactors, step（2）In reaction temperature be 200 DEG C, sample number into spectrum E-3.Evaluation result is shown in Table 2.

Comparative example 4

With embodiment 1, difference is using one section of fixed bed reactors, step（2）In reaction temperature be 150 DEG C, sample number into spectrum E-4.Evaluation result is shown in Table 2.

The feedstock oil main character of table 1.

The evaluation result of table 2.

The evaluation result of table 2 shows, compared with comparative catalyst, using the present invention provide catalyst, for the hydroprocessing processes of lube cut in, when lube base oil pour point is close, C₅ ⁺Liquid is received and lube base oil yield all improves 8wt% or so, and the viscosity index (VI) of product is improved more than 10 units, illustrate catalyst of the present invention during process crude lube stock, and effect is with significantly improving.

Claims (16)

1. the method for two kinds of molecular sieve catalysts of a kind of in-situ one-step synthesis, it is characterised in that including following content：（1）Catalyst precarsor containing amorphous silica-alumina and active metal component is loaded into the upper and lower bed of two sections of insulation fix bed reactors of cold shock formula；（2）The aqueous solution containing diamine compounds is passed through, the catalyst precarsor haptoreaction with upper and lower two beds：Wherein upper bed layer temperature is 195 ~ 215 DEG C, and lower bed layer temperature is 145 ~ 165 DEG C；（3）Material in reactor is again through oxygen-containing gas process, then pass to aqueous ammonium nitrate solution haptoreaction, then pass to nitrogen to be processed, the gas activation for being finally passed through hydrogen is processed, the catalyst of the surface for ZSM-5 molecular sieve of upper bed layer is obtained, the surface of lower bed layer is the catalyst of ZSM-22 molecular sieves.

2. in accordance with the method for claim 1, it is characterised in that：Step（1）Described catalyst precarsor has following property：The SiO of described amorphous silicon aluminium₂And Al₂O₃Mol ratio be 5 ~ 200；Described active metal component is platinum or/and palladium, and on the basis of total catalyst weight, active component content is calculated as 0.1% ~ 10% with metal.

3. in accordance with the method for claim 1, it is characterised in that：Step（1）Described reactor has two sections of insulation fix bed reactors of cold shock formula of cold shock gas using centre, and catalyst precarsor is loaded into respectively in upper and lower two reactor beds, and the reaction temperature of upper and lower two beds is controlled by cold shock gas.

4. in accordance with the method for claim 1, it is characterised in that：Step（2）The diamine compounds are the diamines that carbon number is C5 ~ C8.

5. according to the method described in claim 1 or 4, it is characterised in that：Step（2）Described diamine compounds concentration in aqueous is 0.01 ~ 2mol/L.

6. in accordance with the method for claim 1, it is characterised in that：Step（2）The described inlet amount containing the diamine compounds aqueous solution is 0.1 ~ 10 with catalyst volume ratio.

7. in accordance with the method for claim 1, it is characterised in that：Step（2）Described haptoreaction condition is：Reaction pressure is 0.2 ~ 10MPa, and the reaction time is 12 ~ 100 hours；Upper bed layer reaction temperature is 195 ~ 215 DEG C, and lower bed layer reaction temperature is 145 ~ 165 DEG C.

8. in accordance with the method for claim 1, it is characterised in that：Step（2）Described haptoreaction condition is：Reaction pressure is 0.5 ~ 5MPa, and the reaction time is 24 ~ 72 hours；Upper bed layer reaction temperature is 200 ~ 210 DEG C, and lower bed layer reaction temperature is 150 ~ 160 DEG C.

9. in accordance with the method for claim 1, it is characterised in that：Step（3）The described oxygen-containing gas treatment conditions that are passed through are：Treatment temperature is 400 ~ 600 DEG C, gas agent volume ratio 100 ~ 1000, and process time is 4 ~ 12 hours；Wherein described oxygen-containing gas is the one kind in the mixture of air, oxygen and nitrogen or the mixture of oxygen and inert gas, and oxygen volume fraction in the gas phase is 5% ~ 50%.

10. in accordance with the method for claim 1, it is characterised in that：Step（3）The inlet amount of the aqueous solution containing ammonium nitrate is 0.1 with the volume ratio of catalyst:1~10:1, the wherein mass percent concentration of aqueous ammonium nitrate solution is 16% ~ 50%.

11. in accordance with the method for claim 1, it is characterised in that：Step（3）Described haptoreaction condition is：Reaction pressure is 0.2 ~ 10MPa, and reaction temperature is that, less than the boiling temperature of water at this pressure, the reaction time is 1 ~ 24 hour.

12. in accordance with the method for claim 1, it is characterised in that：Step（3）The described nitrogen treatment condition that is passed through is：100 ~ 300 DEG C for the treatment of temperature, gas agent volume ratio 100 ~ 1000, the time is 4 ~ 12 hours.

13. in accordance with the method for claim 1, it is characterised in that：Step（3）The hydrogen gas can be pure hydrogen or the hydrogen containing inert gas, and the hydrogen volume degree wherein in hydrogen-containing gas is 5% ~ 100%；Described activation process condition is：Pressure is 0.2 ~ 10MPa, and temperature is 200 DEG C ~ 600 DEG C, and the time is 0.5 ~ 24 hour.

14. in accordance with the method for claim 1, it is characterised in that：In step（3）Afterwards, reaction mass is passed directly into in reactor, carries out paraffin hydrocarbon selective isomerization reaction.

15. catalyst for obtaining in accordance with the method for claim 1 are applied to paraffin hydrocarbon and select type isomerization reaction, it is characterised in that：Process conditions are as follows：0.5 ~ 4.0h of volume space velocity^-1, reaction temperature is 200 ~ 400 DEG C, and reaction pressure is 2 ~ 20MPa, and hydrogen hydrocarbon mol ratio is 2 ~ 10.

16. catalyst for obtaining in accordance with the method for claim 1 are applied to paraffin hydrocarbon and select type isomerization reaction, it is characterised in that：Paraffin hydrocarbon selects the feedstock oil wax content 50% ~ 80% for being used in type isomerization reaction.