CN104248964B - A kind of preparation method of Hydrobon catalyst - Google Patents

Abstract

The present invention relates to the preparation method of a kind of Hydrobon catalyst；Tetraethyl orthosilicate, red fuming nitric acid (RFNA), plan thin water aluminium are mixed to get complex carrier SiO₂‑Al₂O₃；By SiO₂‑Al₂O₃Complex carrier adds (NH₄)₆Mo₇O₂₄·4H₂O solution impregnates, obtains support type MoO₃/SiO₂‑Al₂O₃；By MoO₃/SiO₂‑Al₂O₃Add Ni (H₂PO₂)₂Solution impregnates, crystallization in Ar atmosphere is enclosed, obtain support type Ni₂P‑MoO₃/SiO₂‑Al₂O₃；Use H₂S、H₂Gaseous mixture carries out In-situ sulphiding process to its prepared, and obtains Ni₂P‑MoS₂/SiO₂‑Al₂O₃Catalyst；The catalyst that a process for preparing has hydrodesulfurization activity and the stability of excellence, has the highest hydrodesulfurization activity to model compound DBT.

Description

A kind of preparation method of Hydrobon catalyst

Technical field

The present invention relates to the preparation method of a kind of Hydrobon catalyst.

Background technology

The research of Hydrobon catalyst is concentrated mainly on three aspects: (1) improves the loading method of active component;(2) sieve Select active higher component;(3) more preferable carrier is found.This patent is for the exploitation of efficient deep hydrodesulfurizationof catalyst Research is concentrated mainly on searching to be had higher hydrodesulfurization activity component and selection or manufactures two sides of more preferable carrier Face.

Transition metal phosphide especially nickel phosphide in hydrogen-involved reaction, has the catalytic performance of excellence, and has higher Selection C-N and C-S key hydrogenolysis activity, it has also become a new focus in Study of Novel Catalyst field.Prepared Crossing the most traditional method of metal phosphide is temperature-programmed reduction method (TPR), is with phosphate as precursor, in hydrogen Temperature programmed reduction obtains.Prepare phosphide in this way have to rupture the highest P-O key of bond energy in phosphate, So that higher final state temperature, typically more than 550 DEG C.Higher reduction temperature easily causes active component Ni₂P gathering on carrier.And, for the carrier conventional to some, at these elevated temperatures, Ni is easy to and carries Body generation strong interaction, even reaction are (such as: with Al₂O₃Reaction generates Ni (AlO₂)₂).Therefore, how to drop Low synthesis temperature is Ni₂The main direction of studying of P catalyst preparation science.The present invention is from reducing reaction temperature and simplification Operating process is started with, and using ortho phosphorous acid nickel is phosphorus source, replaces traditional phosphate, under an argon at Low Temperature Thermal Reason prepares the new method of metal phosphide.Meanwhile, by prepared Ni₂MoO after P and ammonium molybdate roasting direct₃ Combine, prepare desulphurizing activated component Ni of novel hydrogenation₂P-MoS₂, both combinations can be played in performance Synergy.

This patent is by Ni₂P-MoS₂Active component is supported on SiO₂-Al₂O₃On complex carrier, the most both can be abundant Play Ni₂P/SiO₂High desulfurization activity, it is also possible to utilize at γ-Al₂O₃The scattered SiO of carrier surface₂Weaken Ni₂P With γ-Al₂O₃The strong interaction on surface, can also utilize can being applicable to of mechanical performance and better economy simultaneously The big pore volume γ-Al of oil product₂O₃For carrier.Ni₂P-MoS₂/SiO₂-Al₂O₃New catalyst has DBT excellence Hydrodesulfurization activity.

Summary of the invention

The present invention relates to the preparation method of a kind of Hydrobon catalyst, commonly use macropore Al with industry₂O₃Modified SiO₂-Al₂O₃Complex carrier is carrier, the MoO after ammonium molybdate roasting₃, ortho phosphorous acid nickel phosphorus source is directly in argon atmospher Enclose the Ni that lower Low Temperature Heat Treatment obtains₂P step load successively is at SiO₂-Al₂O₃On complex carrier, by phosphide, sulphur Compound, the advantage of complex carrier combine, and prepares hydrodesulfurization activity and the stability with excellence Ni₂P-MoS₂/SiO₂-Al₂O₃Catalyst, such catalyst has the highest hydrodesulfurization to oil model thing DBT Activity.

The preparation method of a kind of Hydrobon catalyst of the present invention, it is characterised in that: specifically comprise the following steps that

(1) preparation tetraethyl orthosilicate and absolute ethyl alcohol mixed solution are designated as A, preparation absolute ethyl alcohol, deionized water and Red fuming nitric acid (RFNA) mixed solution is designated as B, B solution is added drop-wise in solution A generate the colloidal sol of white, by prepared colloidal sol Pour in the making beating liquid intending thin water aluminium, quickly stir, take out and be placed in clean surface plate, naturally dry, be placed on Baking oven is dried, is placed on Muffle kiln roasting, obtains complex carrier SiO₂-Al₂O₃；

Described tetraethyl orthosilicate absolute ethyl alcohol deionized water red fuming nitric acid (RFNA) mol ratio is 1:9:2:0.3；

Described solution A is the half of required ethanol total amount with the absolute ethyl alcohol in B solution；

Described SiO₂-Al₂O₃SiO in complex carrier₂Load quality is 5-20%；

(2) by (NH₄)₆Mo₇O₂₄·4H₂O dissolves in deionized water, by SiO₂-Al₂O₃Complex carrier adds Impregnating in solution, solution evaporates at room temperature, and is dried, and obtains the precursor of white, white precursor is put into Muffle Kiln roasting, obtains support type MoO₃/SiO₂-Al₂O₃；Dry temperature and be 50-100 DEG C；Sintering temperature is 250-500℃；Roasting time is 2-4h；MoS₂Mass fraction is the 5-10% of carrier；

(3) by Ni (H₂PO₂)₂Dissolve in deionized water, by MoO₃/SiO₂-Al₂O₃Add in solution and impregnate, Evaporate at room temperature, and be dried, obtain the precursor of yellow, precursor is placed in crystallization furnace, be constantly passed through Ar gas, In Ar atmosphere is enclosed, crystallization furnace is risen to 300 DEG C of degree and keeps；Under the protection of Ar gas, crystallization furnace is down to room temperature, Obtain support type Ni₂P-MoO₃/SiO₂-Al₂O₃；The speed of temperature-rise period is at 10-30 DEG C/min；Ni₂P mass is divided Number is the 1-3% of carrier；

(4) H is used₂S、H₂The gaseous mixture support type Ni to preparation₂P-MoO₃/SiO₂-Al₂O₃Sample is carried out in situ Vulcanizing treatment, obtains Ni₂P-MoS₂/SiO₂-Al₂O₃Catalyst；

H₂The volume fraction of S is 10%, and flow velocity is 30-40ml/min, cure time 3h.

The Ni that a process for preparing₂P-MoS₂/SiO₂-Al₂O₃Catalyst different from other Hydrobon catalysts it Place is, this catalyst employs a kind of macropore Al₂O₃Modified SiO₂-Al₂O₃Complex carrier is carrier, with Time ammonium molybdate roasting after MoO₃Directly under argon atmosphere, Low Temperature Heat Treatment obtains with ortho phosphorous acid nickel phosphorus source Ni₂The compounding ingredients Ni of P composition₂P-MoS₂As active component, this catalyst is by phosphide, sulfide, compound The advantage of carrier combines, and has the highest hydrodesulfurization activity to model compound DBT.

Detailed description of the invention

Embodiment 1

It is formulated as follows solution:

Tetraethyl orthosilicate (TEOS) absolute ethyl alcohol deionized water red fuming nitric acid (RFNA)=1:9:2:0.3(mol ratio)

Beaker A:12.5ml tetraethyl orthosilicate (TEOS)+15ml absolute ethyl alcohol (sequential write is addition sequence)

Beaker B:15ml absolute ethyl alcohol+2ml deionized water+1ml red fuming nitric acid (RFNA) (sequential write is addition sequence)

The half of required ethanol total amount (absolute ethyl alcohol in beaker A and beaker B be)

Solution in beaker B is added drop-wise in beaker A generate with 20ml/min speed the colloidal sol of white, will at once The colloidal sol prepared is poured in the making beating liquid intending thin water aluminium, quickly stirs 60min, takes out and is placed in clean surface plate, Naturally dry 24h, put 120 DEG C of drying 3h in an oven, be placed on 500 DEG C of roasting 4h in Muffle furnace.It is combined Carrier S iO₂-Al₂O₃。

By 0.13g(NH₄)₆Mo₇O₂₄·4H₂O is dissolved in a certain amount of deionized water, by 1g SiO₂-Al₂O₃ Carrier adds dipping in above-mentioned solution, evaporates at room temperature, and is dried under the conditions of 80 DEG C, is placed in Muffle furnace 500 DEG C of roasting 4h, prepare MoO₃/SiO₂-Al₂O₃。

By 0.1gNi (H₂PO₂)₂It is dissolved in a certain amount of deionized water, by 1.1g carrier (MoO₃/SiO₂-Al₂O₃) Add in above-mentioned solution and impregnate, evaporate at room temperature, and be dried under the conditions of 80 DEG C, obtain the precursor of yellow.Will Precursor is placed in crystallization furnace, is constantly passed through Ar gas.In Ar atmosphere is enclosed, crystallization furnace is risen to 300 DEG C and keeps 2h. Under the protection of Ar gas, crystallization furnace is down to room temperature, i.e. obtains support type and prepares Ni₂P-MoO₃/SiO₂-Al₂O₃。

The support type Ni of preparation₂P-MoO₃/SiO₂-Al₂O₃. at a certain temperature with containing H₂S volume fraction is 10% H₂S、H₂Gaseous mixture carries out In-situ sulphiding process 3h to sample, prepares MoS₂Mass fraction is 10%, Ni₂P matter Amount mark is 3%Ni₂P-MoS₂/SiO₂-Al₂O₃New catalyst, is designated as catalyst A.

Embodiment 2

The same with catalyst A preparation process, prepare MoS₂Mass fraction is 10%, Ni₂P mass fraction is 5% Ni₂P-MoS₂/SiO₂-Al₂O₃New catalyst, is designated as catalyst B.

Embodiment 3

The same with catalyst A preparation process, prepare MoS₂Mass fraction is 10%, Ni₂P mass fraction is 10% Ni₂P-MoS₂/SiO₂-Al₂O₃New catalyst, is designated as catalyst C.

Embodiment 4

The same with catalyst A preparation process, prepare MoS₂Mass fraction is 5%, Ni₂P mass fraction is 3% Ni₂P-MoS₂/SiO₂-Al₂O₃New catalyst, is designated as catalyst D.

Comparative example 1 is the same with catalyst A preparation process, but carrier changes Al into₂O₃, prepare MoS₂Mass fraction is 5%,

Ni₂P mass fraction is the Ni of 3%₂P-MoS₂/Al₂O₃New catalyst, is designated as catalyst E.

Comparative example 2MoO₃/SiO₂-Al₂O₃Catalyst A preparation process is the same, with MoO₃/SiO₂-Al₂O₃For carrying Body, adds a certain amount of Ni (NO₃)₂, 500 DEG C of Muffle kiln roasting 4h prepare NiO-MoO₃/SiO₂-Al₂O₃。 NiS-MoS is prepared with the conditions of vulcanization catalyst A preparation₂/SiO₂-Al₂O₃, it is designated as catalyst F.

Above-mentioned a few class catalyst are carried out hydrodesulfurization performance evaluation.It is in homemade tubular type that the HDS of this patent evaluates Carrying out on pressurization static bed continuous flow reactor, with dibenzothiophenes as probe, used raw material is that quality is divided Number is 0.3wt% dibenzothiophenes (DBT)/decahydronaphthalene mixed solution, regulates H₂Pressure 3.0Mpa, flow velocity is 150-160ml/min, with 5h^-1Liquid hourly space velocity (LHSV) charging, react at 250 DEG C, reaction conversion ratio situation such as table 1.

Table 1

Catalyst	Dibenzothiophenes conversion ratio
		A	96%
B	65%
		C	60%
D	85%
		E	86%
F	89%

Claims (1)

1. the preparation method of a Hydrobon catalyst, it is characterised in that:

(1) preparation tetraethyl orthosilicate and absolute ethyl alcohol mixed solution are designated as A, and preparation absolute ethyl alcohol, deionized water and red fuming nitric acid (RFNA) mix Close solution and be designated as B, B solution is added drop-wise in solution A generate the colloidal sol of white, prepared colloidal sol is poured into and intends beating of thin water aluminium In slurries, quickly stir, take out and be placed in clean surface plate, naturally dry, put and dry in an oven, be placed in Muffle furnace Roasting, obtains complex carrier SiO₂-Al₂O₃；

Described tetraethyl orthosilicate: absolute ethyl alcohol: deionized water: red fuming nitric acid (RFNA) mol ratio is 1:9:2:0.3；

Described solution A is the half of required ethanol total amount with the absolute ethyl alcohol in B solution；

Described SiO₂-Al₂O₃SiO in complex carrier₂Load quality is 5-20%；

(2) by (NH₄)₆Mo₇O₂₄·4H₂O dissolves in deionized water, by SiO₂-Al₂O₃Complex carrier adds dipping in solution, Solution evaporates at room temperature, and is dried, and obtains the precursor of white, white precursor is put into Muffle kiln roasting, obtains support type MoO₃/SiO₂-Al₂O₃；Dry temperature and be 50-100 DEG C；Sintering temperature is 250-500 DEG C；Roasting time is 2-4h；MoO₃Matter Amount mark is the 5-10% of carrier；

(3) by Ni (H₂PO₂)₂Dissolve in deionized water, by MoO₃/SiO₂-Al₂O₃Add in solution and impregnate, at room temperature Evaporation, and be dried, obtain the precursor of yellow, precursor is placed in crystallization furnace, be constantly passed through Ar gas, will in Ar atmosphere is enclosed Crystallization furnace rises to 300 DEG C of degree and keeps；Under the protection of Ar gas, crystallization furnace is down to room temperature, obtains support type Ni₂P-MoO₃/SiO₂-Al₂O₃；The speed of temperature-rise period is at 10-30 DEG C/min；Ni₂P mass fraction is the 1-3% of carrier；

(4) H is used₂S、H₂The gaseous mixture support type Ni to preparation₂P-MoO₃/SiO₂-Al₂O₃Sample carries out In-situ sulphiding process, Obtain Ni₂P-MoS₂/SiO₂-Al₂O₃Catalyst；

H₂The volume fraction of S is 10%, and flow velocity is 30-40ml/min, cure time 3h.