CN101837294A

CN101837294A - Preparation method for solid acid catalyst r-AI203

Info

Publication number: CN101837294A
Application number: CN 201010142647
Authority: CN
Inventors: 张振学; 张永锐
Original assignee: Bazhou Dongchen Industry & Trade Co Ltd
Current assignee: Bazhou Dongchen Industry & Trade Co Ltd
Priority date: 2010-03-03
Filing date: 2010-03-03
Publication date: 2010-09-22

Abstract

The invention provides a preparation method for catalyst r-AI203 in the productive process of methyl alcohol, which sequentially comprises the following steps that: under the temperature condition of 500 DEG C to 550 DEC temperature condition, a reacting furnace is used for roasting r-AI203 carrier for 4-5 hours; nickel acetate, ammonium molybdate and hexamine is dissolved in ammonia water with 30% of percentage concentration to prepare clear impregnating liquid, is stirred and soaked in the room temperature for 2-4 hours, filtered and dried, dried in the vacuum for 5-8 hours in the temperature of 60 DEG C-100 DEG C, compressed and mould by a tablet machine, sieved and filtered; and then the r-AI203 carrier is baked in a reacting furnace which is risen to 450 DEG C to 550 DEG C; the baked r-AI203 is for four hours to obtain a catalyst in the nitrogen containing 1% of oxygen according to the volume percent, wherein the mass percents of the nickel and the molybdenum in the active components are respectively 25-10% and 6-25%; and the nickel and the molybdenum exist in the coexisting form of the Ni2M03N and less oxides. The catalyst prepared by the method is characterized by long service life and good activity and heat stability; the dehydration reaction selectivity is above 99%; the catalyst can increase the conversion rate of dimethyl ether to methanol and the purity of the methanol, well solves the problem that in the process of producing methanol production with sulphate process, the device is corroded and the residual liquid is seriously polluted.

Description

A kind of solid acid catalyst r-Al 2O 3The preparation method

Technical field

The present invention relates to a kind of chemical catalyst, especially for the Preparation of catalysts method in the methanol process.

Background technology

Methyl alcohol is a kind of very important raw material of industry.At present, mainly be to produce dimethyl ether through series of chemical, and then be methyl alcohol with dimethyl ether conversion.The production method of dimethyl ether mainly contains sulfuric acid process, methanol vapor phase catalytic dehydration, the direct dimethyl ether synthesis method of one-step method from syngas.Though sulfuric acid process reaction condition gentleness, methyl alcohol conversion per pass height is higher, generally more than 85%, both producing can be intermittently, also can be continuous, but equipment corrosion is serious in the production process, raffinate and waste water environmental pollution are very serious, the operating condition harshness, and the methyl alcohol of producing is difficult to remove trace impurity, therefore peculiar smell, poor product quality are arranged, and the catalyst life cycle is short.With synthesis gas (H ₂+ CO) though the production technology of one-step method direct method dimethyl ether synthesis has application, and is still immature at present.

Summary of the invention

The object of the present invention is to provide a kind of catalyst r-AL for methanol process ₂O ₃The preparation method, use the Production By Sulfuric Acid Process process adopt this catalyst can better solve equipment corrosion serious, reduce the problem that raffinate pollutes.Simultaneously, can improve the purity that dimethyl ether conversion is conversion of methanol and methyl alcohol.This catalyst has long service life, the characteristics of activity, Heat stability is good, and the dehydration selectivity is more than 99%.

Purpose of the present invention realizes by the following technical solutions:

The carrier roasting is under 500 ℃ of-550 ℃ of temperature conditions, with reacting furnace roasting r-AL ₂O ₃Carrier 4-5 hour;

Maceration extract dipping: with mol ratio be 14: 3: 17.2～14: 13: 27 nickel acetate, ammonium molybdate and hexa to be dissolved in percent concentration be to make the clarification maceration extract in 30% the ammoniacal liquor, then will be through r-AL after the roasting ₂O ₃Carrier joins in the maceration extract, stirs dipping under the room temperature and filters after 2-4 hour, fully dries;

Dry, moulding: the r-AL after will drying ₂O ₃The tablet press machine compression forming is used in carrier vacuum drying 5～8 hours under 60 ℃～100 ℃ temperature conditions, uses screen filtration;

Again roasting: with the r-AL after the molding filter ₂O ₃Carrier is warming up to 450 ℃～550 ℃ condition roastings in reacting furnace;

Passivation Treatment: will be again r-AL after the roasting ₂O ₃Carrier contains at percentage by volume that passivation obtained catalyst after 4 hours in the nitrogen of oxygen 1%, and the mass percent of its each active component is: nickel 25-10%, molybdenum 6-25%, and nickel and molybdenum are with ALONi ₂Mo ₃The form of N and a small amount of oxide coexistence exists.

The specific embodiment

Further specify Preparation of catalysts method involved in the present invention below in conjunction with embodiment.

Embodiment one:

Under 520 ℃ of temperature conditions, with reacting furnace roasting r-AL ₂O ₃Carrier 4 and a half hours; Be that to be dissolved in percent concentration be to make the clarification maceration extract in 30% the ammoniacal liquor for 14: 3: 20 nickel acetate, ammonium molybdate and hexa with mol ratio; With r-AL ₂O ₃Carrier joins in the maceration extract, stirs dipping under the room temperature and filters after two and one-half-hours, dries; Under 75 ℃ of temperature conditions, use then vacuum drying 6 hours, use the tablet press machine compression forming, use screen filtration; Then roasting under right temperature conditions about 500 ℃ in reacting furnace; At last with the r-AL after the roasting ₂O ₃Carrier contains at percentage by volume that passivation obtained catalyst after 4 hours in the nitrogen of oxygen 1%.

Embodiment two:

Under 540 ℃ of temperature conditions, with reacting furnace roasting r-AL ₂O ₃Carrier 5 hours; Be that to be dissolved in percent concentration be to make the clarification maceration extract in 30% the ammoniacal liquor for 14: 3: 25 nickel acetate, ammonium molybdate and hexa with mol ratio; With r-AL ₂O ₃Carrier joins in the maceration extract, stirs dipping under the room temperature and filters after 3 and a half hours, dries; Under 90 ℃ of temperature conditions, use then vacuum drying 7 hours, use the tablet press machine compression forming, use screen filtration; Then roasting under 480 ℃ of left and right sides temperature conditions in reacting furnace; At last with the r-AL after the roasting ₂O ₃Carrier contains at percentage by volume that passivation obtained catalyst after 4 hours in the nitrogen of oxygen 1%.

Claims

1. solid acid catalyst r-AL ₂O ₃The preparation method, it is characterized in that: successively to r-AL ₂O ₃Carrier roasting, maceration extract dipping, filter dry, drying and moulding, again roasting, nitrogen passivation process obtain catalyst.

2. solid acid catalyst r-AL as claimed in claim 1 ₂O ₃The preparation method, it is characterized in that: r-AL ₂O ₃Carrier is used reacting furnace roasting 4-5 hour under 500 ℃ of-550 ℃ of temperature conditions; Maceration extract is dissolved in the ammoniacal liquor with nickel acetate, ammonium molybdate and hexa and makes; R-AL after the roasting ₂O ₃Carrier floods in maceration extract after 2-4 hour and to filter, to dry, again vacuum drying 5～8 hours under 60 ℃～100 ℃ temperature; Then roasting under 450 ℃～550 ℃ conditions of reacting furnace temperature; With the r-AL after the roasting ₂O ₃Carrier is used nitrogen Passivation Treatment 4 hours.

3. solid acid catalyst r-AL as claimed in claim 1 or 2 ₂O ₃The preparation method, it is characterized in that: the nickel acetate, ammonium molybdate and the hexa that are used for the preparation maceration extract are 14: 3: 17.2～14: 13: 27 by the mole concentration ratio; The percent concentration of ammoniacal liquor is 30%; By volume the percentage meter is used for Passivation Treatment r-AL ₂O ₃The oxygen content 1% of the nitrogen of carrier.

4. such as claim 1 or 2 or 3 described solid acid catalyst r-AL ₂O ₃The preparation method, it is characterized in that: by the quality percentage, nickel 25-10%, molybdenum 6-25% in the active component of the catalyst that makes, and nickel and molybdenum are with Ni ₂Mo ₃The form of N and a small amount of oxide coexistence exists.