CN100395023C

CN100395023C - Catalyst for synthesizing copper based methanol and preparing method

Info

Publication number: CN100395023C
Application number: CNB2004100660845A
Authority: CN
Inventors: 刘金辉; 仇冬; 曹建平; 黄金钱; 赵蔡斌
Original assignee: Research Institute of Nanjing Chemical Industry Group Co Ltd
Current assignee: Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
Priority date: 2004-12-17
Filing date: 2004-12-17
Publication date: 2008-06-18
Anticipated expiration: 2024-12-17
Also published as: CN1660493A

Abstract

The present invention relates to a novel copper-base catalyst for synthesizing methanol and a preparation method thereof, which belongs to the technical field of catalysts. The novel copper-base catalyst for synthesizing methanol is prepared from main components and minor components, wherein the main components comprise copper-zincum active precursors, and the minor components comprise carriers with high thermal stability and high surface activity; the preparation method comprises: the copper-zincum active precursors and the carriers with high thermal stability and high surface activity are respectively prepared, and then the precursors and the carriers are mixed and prepared into the novel copper-base catalyst for synthesizing methanol. Compared with the catalyst prepared by the traditional method, the novel copper-base catalyst for synthesizing methanol of the present invention has larger specific surface area, higher methanol synthesis activity and higher thermal stability.

Description

Catalyst for synthesizing copper based methanol and preparation method thereof

Technical field:

The invention belongs to the catalyst class, relate to a kind of preparation method of high strength high activity catalyst for synthesizing copper based methanol.

Background technology:

Methyl alcohol is one of the most basic Organic Chemicals.In recent years, methyl alcohol demand and production capacity sustainable growth, the purposes of methyl alcohol also has new development.Plant-scale methyl alcohol generally is with containing H ₂, CO, CO ₂The synthesis gas method production of under certain pressure and temperature and the condition that has catalyst to exist, reacting.In early days, people are that the catalyst of main active ingredient is produced methyl alcohol in order to the oxide of Zn, Cr, but this catalyst must just can have active preferably under the condition of high temperature (as 350 ℃) and high pressure (as 30.0MPa), thereby the methanol contaminant content height of producing, and energy consumption is also high.Afterwards, it is found that the Cu-Zn-Al series catalysts has good low-temp methanol synthesizing activity, the oxide of cupric, zinc is called as reactive precursor, and aluminium oxide is the heat endurance material, is used as carrier.Because this system low temperature active is good, the methanol contaminant content of Huo Deing is lower at low temperatures, and this catalyst also has the excellent methanol synthesizing activity under lower operating pressure, helps energy-conservationly, and this system is widely used.

The existing manufacture method of catalyst for methanol:

Methanol synthesis catalyst is generally copper-zinc-aluminium system at present, and some products also may add the 4th component such as V, Mn etc., but content is less.Common preparation method is the soluble-salt mixed solution and the precipitating reagent reaction of copper, zinc, the copper that obtains, zinc precipitation add the inert carrier aluminium oxide again, make catalyst (as Chinese patent ZL 00133276.7 and ZL 00133277.5) through operations such as washing, filtration, oven dry, roasting, moulding.The soluble-salt of copper, zinc has nitrate, acetate etc.Precipitating reagent can be carbonate (sodium, potassium, an ammonium etc.), also can be NaOH, potassium hydroxide, ammoniacal liquor etc.The adding form of aluminium oxide can be the finished product aluminium oxide, and also aluminium hydroxide is perhaps with the method adding of aluminum soluble salt with the soluble-salt mixed solution co-precipitation of copper, zinc.Catalyst for methanol production intensity with the method preparation is low, and heat endurance is relatively poor, and the life-span is short.

Summary of the invention:

The objective of the invention is to propose a kind of new catalyst for methanol manufacture method.Methanol synthesis catalyst with the inventive method manufacturing has the bigger specific surface of catalyst for preparing than conventional method, shows higher methyl alcohol synthesizing activity and heat endurance.Catalyst for synthesizing copper based methanol of the present invention, the Main Ingredients and Appearance that contains are copper, zinc reactive precursor, it is characterized in that it also contains the less important composition of the big surface-active carrier of heat endurance;

Its preparation method is to prepare the big surface-active carrier of copper, zinc reactive precursor and heat endurance respectively, mixes then and makes catalyst.

1L is contained the solution of 5-200g soluble copper salt and 5-200g soluble zinc salt and the carbonate solution of concentration 20～200g/L neutralizes, N-process control temperature is at 60-85 ℃, and control endpoint pH 6.8-7.2 obtains copper, zinc reactive precursor slip thus; The carbonate solution that 1L is contained 5-50g soluble copper salt and 5-200g/L soluble aluminum salting liquid and concentration 20～200g/L neutralizes, N-process control temperature is at 60～85 ℃, control endpoint pH 6.8～7.2, again this gel slip is mixed with copper, zinc reactive precursor slip, washing then after filtration,, the filter cake that obtains is 80-120 ℃ of oven dry, and again at 280-320 ℃ of roasting 2-4hr., the catalyst after the roasting is admixed graphite and is pressed into tablet and is finished catalyst.

Above-mentioned soluble-salt can be nitrate or acetate; Aluminum nitrate, copper nitrate solution also can replace, but can not contain Cl, S etc. with other aluminum soluble salt, copper salt solution.Carbonate is sodium carbonate or potash.

The specific embodiment:

Below further specify content of the present invention by Comparative Examples and embodiment:

Comparative Examples 1-1

1L is contained 120gCu (NO ₃) ₂And 115gZn (NO ₃) ₂Solution as solution A, with 135gNa ₂CO ₃Be dissolved in the 3L deionized water and make solution B.Under stirring solution A is added solution B, N-process control temperature is controlled endpoint pH 6.8～7.2 at 60～85 ℃.The slip that obtains thus adds 6.4g Al ₂O ₃, then after filtration, washing, the filter cake that obtains is 115 ℃ of oven dry, and again at 300 ℃ of roasting 3hr., the catalyst after the roasting is admixed graphite and is pressed into tablet and is finished catalyst.

Embodiment 1-2

1L is contained 110gCu (NO ₃) ₂And 115gZn (NO ₃) ₂Solution as solution A, with 135gNa ₂CO ₃Be dissolved in the 3L deionized water and make solution B.Under stirring solution A is added solution B, N-process control temperature is controlled endpoint pH 6.8～7.2 at 60～85 ℃.Obtain copper, zinc reactive precursor slip thus.1L is contained 10gCu (NO ₃) ₂And 40gAl (NO ₃) ₃Solution as C solution.160g potash is dissolved in the 2L deionized water makes solution D.Under stirring solution C is added solution D, N-process control temperature is controlled endpoint pH 6.8～7.2 at 60～85 ℃.Again this gel slip is mixed with copper, zinc reactive precursor slip.Then after filtration, washing, the filter cake that obtains is 115 ℃ of oven dry, again at 300 ℃ of roasting 3hr., the catalyst after the roasting is admixed graphite and is pressed into tablet and is finished catalyst.

Comparative Examples 2-1

1L is contained 150gCu (NO ₃) ₂And 83gZn (NO ₃) ₂Solution as solution A, with 135gNa ₂CO ₃Be dissolved in the 3L deionized water and make solution B.Under stirring solution A is added solution B, N-process control temperature is controlled endpoint pH 6.8～7.2 at 60～85 ℃.The slip that obtains thus adds 4.6gAl ₂O ₃, then after filtration, washing, the filter cake that obtains is 115 ℃ of oven dry, and again at 300 ℃ of roasting 3hr., the catalyst after the roasting is admixed graphite and is pressed into tablet and is finished catalyst.

Embodiment 2-2

1L is contained 130gCu (NO ₃) ₂And 83gZn (NO ₃) ₂Solution as solution A, with 135gNa ₂CO ₃Be dissolved in the 3L deionized water and make solution B.Under stirring solution A is added solution B, N-process control temperature is controlled endpoint pH 6.8～7.2 at 60～85 ℃.Obtain copper, zinc reactive precursor slip thus.1L is contained 20gCu (NO ₃) ₂And 40gAl (NO ₃) ₃Solution as C solution.160g potash is dissolved in the 2L deionized water makes solution D.Under stirring solution C is added solution D, N-process control temperature is controlled endpoint pH 6.8～7.2 at 60～85 ℃.Again this gel slip is mixed with copper, zinc reactive precursor slip.Then after filtration, washing, the filter cake that obtains is 115 ℃ of oven dry, again at 300 ℃ of roasting 3hr., the catalyst after the roasting is admixed graphite and is pressed into tablet and is finished catalyst.

Comparative Examples 3-1

1L is contained 160gCu (NO ₃) ₂And 72gZn (NO ₃) ₂Solution as solution A, with 135gNa ₂CO ₃Be dissolved in the 3L deionized water and make solution B.Under stirring solution A is added solution B, N-process control temperature is controlled endpoint pH 6.8～7.2 at 60～85 ℃.The slip that obtains thus adds 8gAl ₂O ₃., then after filtration, washing, the filter cake that obtains is 115 ℃ of oven dry, and again at 300 ℃ of roasting 3hr., the catalyst after the roasting is admixed graphite and is pressed into tablet and is finished catalyst.

Embodiment 3-2

1L is contained 145gCu (NO ₃) ₂And 72gZn (NO ₃) ₂Solution as solution A, with 135gNa ₂CO ₃Be dissolved in the 3L deionized water and make solution B.Under stirring solution A is added solution B, N-process control temperature is controlled endpoint pH 6.8～7.2 at 60～85 ℃.Obtain copper, zinc reactive precursor slip thus.1L is contained 15gCu (NO ₃) ₂And 45gAl (NO ₃) ₃Solution as C solution, 160g potash is dissolved in the 2L deionized water makes solution D.Under stirring solution C is added solution D, N-process control temperature is controlled endpoint pH 6.8～7.2 at 60～85 ℃.Again this gel slip is mixed with copper, zinc reactive precursor slip.Then after filtration, washing, the filter cake that obtains is at 115 ℃ of oven dry 20hr., again at 300 ℃ of roasting 3hr., the catalyst after the roasting is admixed graphite and is pressed into tablet and is finished catalyst.

Sample test

Catalyst sample: granularity is 0.425-1.180mm.

Sample activation: sample is before the test activity, and (H2: N2=3: 97) reduction, temperature programming to 230 ℃ activates to feed reducing gases.

The active testing condition: the sample after the reduction, feed synthesis gas, at pressure 5.0MPa, 230 ℃ of temperature, air speed 2.0 * 104h ^-1Down, synthetic gas density, % (v/v): CO 3.8～4.2, CO ₂0.7～0.9, H ₂55～65, measure initial activity and (generate the space-time yield gml of methyl alcohol ^-1h ^-1).

Heat-resisting back active testing: after the sample determination initial activity, stand 350 ℃, the heat-resisting processing of 20h, return to again under the above-mentioned condition, measures activity (the space-time yield gml of generation methyl alcohol after heat-resisting ^-1h ^-1) with the height of this activity value with the ratio value representation sample heat endurance of initial activity.

Active testing the results are shown in table 1.Wherein sample 1-2,2-2,3-2 are the catalyst with the preparation of the big surface-active preparing carriers of heat endurance of the present invention method, sample 1-1,2-1,3-1, are respectively the reference catalyst for preparing with corresponding commodity alumina support.

Can find out that by test result all apparently higher than the reference sample, especially heat endurance is better with the catalyst methanol yield of the inventive method preparation and heat endurance.Show that method for preparing catalyst of the present invention compared tangible progress with existing method.

Table 1 active testing result

Claims

1. the preparation method of a catalyst for synthesizing copper based methanol, catalyst for synthesizing copper based methanol is copper-zinc-aluminium system, it is characterized in that preparing respectively the big surface-active carrier of copper, zinc reactive precursor and heat endurance, again the two is mixed with catalyst; 1L is contained the solution of 5-200g soluble copper salt and 5-200g soluble zinc salt and the carbonate solution of concentration 20～200g/L neutralizes, N-process control temperature is at 60-85 ℃, and control endpoint pH 6.8-7.2 obtains copper, zinc reactive precursor slip thus; The carbonate solution that 1L is contained 5-50g soluble copper salt and 5-200g/L soluble aluminum salting liquid and concentration 20～200g/L neutralizes, N-process control temperature is at 60～85 ℃, control endpoint pH 6.8～7.2, again this gel slip is mixed with copper, zinc reactive precursor slip, washing then after filtration,, the filter cake that obtains is 80-120 ℃ of oven dry, and again at 280-320 ℃ of roasting 2-4hr., the catalyst after the roasting is admixed graphite and is pressed into tablet and is finished catalyst; Described carbonate is sodium carbonate or potash.

2. the preparation method of catalyst for synthesizing copper based methanol according to claim 1 is characterized in that soluble-salt is nitrate or acetate.