CN103495426B

CN103495426B - A kind ofly reclaim the method that copper is Waste Catalyst during Methanol Synthesis

Info

Publication number: CN103495426B
Application number: CN201310429333.1A
Authority: CN
Inventors: 周焕文; 黄燕
Original assignee: DALIAN REAK SCIENCE AND TECHNOLOGY Co Ltd
Current assignee: Dalian Ruike Technology Co.,Ltd.
Priority date: 2013-09-22
Filing date: 2013-09-22
Publication date: 2016-05-18
Anticipated expiration: 2033-09-22
Also published as: CN103495426A

Abstract

Reclaiming copper is a method for Waste Catalyst during Methanol Synthesis, belongs to catalyst technical field. The method by copper be Waste Catalyst during Methanol Synthesis after remove impurity make use of physics methods and high-temperature roasting pretreatment, add the excessive catalyst of nitric acid dissolve, obtain containing Cu (NO₃)₂、Zn(NO₃)₂With a small amount of Fe (NO₃)₃Solution. Add the pH value that alkali regulates mixed solution, the metal impurities ion precipitations such as Fe are separated. The copper zinc nitrate solution reclaiming can be directly used in manufacture catalst for synthesis of methanol, and realizing copper is recycling of catalyst for methanol. It is recycling of catalyst for methanol that this recovery method can be realized copper, and heavy metal resources utilization rate is high, and technique is simple, easy to operate, and the expense of recycling is low; The rate of recovery of Cu, Zn is high, can directly be used for preparing new catalyst for methanol; The method that adopts catalyst excess when acid-soluble, nitric acid reaction is complete; Former particle roasting direct and dissolving, loss is few, also can avoid the pollution of dust to air; Can be applicable to various copper is Waste Catalyst during Methanol Synthesis and other CuO/ZnO/Al₂O₃It is the recovery of non-catalyst for methanol.

Description

A kind ofly reclaim the method that copper is Waste Catalyst during Methanol Synthesis

Technical field

The present invention relates to a kind of method that copper is Waste Catalyst during Methanol Synthesis that reclaims, particularly copper is that Waste Catalyst during Methanol Synthesis reclaimsThe method of preparing catalyst for methanol, belongs to catalyst technical field.

Background technology

Methyl alcohol is important large chemical products and Organic Chemicals, and China's methyl alcohol production capacity accounts for two of world's aggregated capacity/ mono-, rank first in the world. Copper be catalyst for methanol due to its high activity and high selectivity, in industry application very wideGeneral. But because copper is catalyst for methanol poor heat resistance, not resistance to sulphur, the easy moisture absorption, easily poisoning, be generally 1-2 its service life, because ofThis has a large amount of copper is every year that waste methanol catalyst produces. This type of waste methanol catalyst is mainly made up of Cu, Zn and Al, and being has heavilyThe heavy metal resources utilized being worth. Reclaiming and making full use of these resources not only can turn waste into wealth, and obtains good warpJi benefit, but also be conducive to environmental protection and improve China's ecological environment.

At present, waste methanol catalyst reclaims the displacement-electrolysis that adopt more, and waste methanol catalyst is changed into copper, zinc metalForm. This method metal recovery utilization rate is low, and produces a large amount of Cu that contains²⁺、Zn²⁺Waste liquid, contaminated environment. SeparatelyOutward, also have waste methanol catalyst is converted into other chemical products, as stannous chloride and zinc oxide, cupric sulfate pentahydrate and active oxygenChange zinc etc. The method of more than recycling all relates to separating of copper and zinc, not only complex process, and the recycling of resourceRate is not high.

CN1258752A discloses a kind of method that reclaims copper and zinc oxide from copper zinc dead catalyst. It is mainly to adoptDead catalyst becomes copper zinc complex with ammino symphysis, filtering iron, aluminium, calcium etc. In cuprammonium, zinc ammonia complex, adding zinc dust precipitation goes outCopper, remaining zinc ammonia complex adds thermal decomposition, makes zinc oxide. In the method removal process, the copper zinc in dead catalyst is dividedFrom, and need add a large amount of zinc to replace copper, process is long, benefit is low. And zinc ammonia complex adds thermal decomposition and prepares zinc oxideTime have a large amount of ammonia to produce, can cause environmental pollution.

CN102125851-A discloses the catalyst based application process of preparing hydrogen from methyl alcohol catalyst of a kind of copper scrap. AdoptCalcining, acidleach, filtering and impurity removing and regeneration four steps, the two kinds of metals of Cu, Zn during copper scrap is catalyst based are recycled, evaporationAfter excessive nitric acid, add required component, for the preparation of hydrogen from methyl alcohol catalyst. Although this kind of method technique is simpler, evaporationExcessive nitric acid, not only pollutes the environment but also wastes resource.

Summary of the invention

The object of the present invention is to provide a kind of major metal component that is Waste Catalyst during Methanol Synthesis by copper to change into nitrate,Be directly used in and prepare catalyst for methanol, realize the method recycling. The rate of recovery of this method copper, zinc more than 90%, productionActivity and selectivity and the industrial catalyst of catalyst for methanol are suitable.

Concrete technical scheme of the present invention: a kind of copper that reclaims is that the method for Waste Catalyst during Methanol Synthesis comprises following steps: a, thingReason removal of impurities: be waste methanol catalyst through screening, magnetic separation process by copper, remove bring into assorted in handling or transfer catalyst processMatter, as iron nail, porcelain ball and other foreign material;

B, high-temperature roasting: be Waste Catalyst during Methanol Synthesis by the copper after remove impurity make use of physics methods, roasting in air atmosphere, removes and usingIn process, be deposited on the organic matter on catalyst, the iron that makes to be deposited on catalyst is transformed into ferric ion, and copper component is completeBe transformed into cupric oxide; Sintering temperature is 800-1000 DEG C, roasting time 3-10 hour;

C, acid-soluble

Be in Waste Catalyst during Methanol Synthesis, to add appropriate nitric acid at the copper after described remove impurity make use of physics methods and calcination steps, stirringMix lower catalyst-solvent, make the metal oxide component of catalyst be transformed into corresponding nitrate solution, catalyzing and synthesizing methyl alcoholThe metal impurities of bringing in process are also transformed into corresponding nitrate solution, obtain after filtration containing Cu (NO₃)₂、Zn(NO₃)₂WithA small amount of Fe (NO₃)₃Solution;

D, precipitate and separate impurity

Regulating the pH value of described nitrate solution with alkaline solution is 3-4, the iron ion in solution is precipitated, thenWith common filtration or sedimentation method separation, the Fe in solution³⁺Concentration controls to below 100 μ g/L.

Described copper is that waste methanol catalyst is the fine particle after former particle or pulverizing.

The concentration of nitric acid used is more than 10% any concentration, and dissolved copper is that the temperature of waste methanol catalyst is 20-80DEG C, copper is that the mass ratio of waste methanol catalyst and nitric acid is 0.1-0.3.

Alkaline solution used is the solution of alkali-metal carbonate, bicarbonate or hydroxide, the concentration of alkaline solutionFor 0.05-2.0mol/L.

Tool of the present invention has the following advantages: it is catalyst for methanol that the method that this recovery copper is Waste Catalyst during Methanol Synthesis can realize copperRecycle, heavy metal resources utilization rate is high, technique is simple, easy to operate, the expense of recycling is low, is easy to industrialization;The rate of recovery of Cu, Zn is high, and copper zinc, than basically identical with raw catalyst, can directly be used for preparing new catalyst for methanol easily;The method that adopts catalyst excess when acid-soluble, nitric acid reaction is complete, and nitric acid dosage is saved; Catalyst granules is without pulverizing, formerGrain roasting direct and dissolving, loss is few, also can avoid the pollution of dust to air; Can be applicable to various copper is Waste Catalyst during Methanol SynthesisWith other CuO/ZnO/Al₂O₃It is the recovery of non-catalyst for methanol.

Detailed description of the invention

Table 1 lists the composition of a class catalyst for methanol after before use. Data from table can be clear that, copperBe catalyst for methanol after long use, Cu, Zn, Al content are little, be mainly increased catalyst harmfulIron, sulfide and organic matter.

Table 1: a class copper is that methyl alcohol is new, the dead catalyst composition table of comparisons

Embodiment 1

A kind of copper is Waste Catalyst during Methanol Synthesis, and it consists of (w%): CuO:60, ZnO:28, S:1.6, Al₂O₃：8.0，Fe(Fe₂O₃): 0.2, graphite: 2.0, C_xH_y: 0.2. By this dead catalyst after remove impurity make use of physics methods at 900 DEG C of roasting 5h. Take 15g roastingDead catalyst after burning, adds 80ml20%HNO₃. 50 DEG C of stirring reactions 1 hour, filter and obtain the transparent filtrate of navy blue,Add 4%NaHCO₃Solution, regulates pH=3.6. Now Fe in solution³⁺Content is 0.05 μ g/L, [Cu²⁺]=73.21g/L，[Zn²⁺]34.05g/L，[Cu²⁺]/[Zn²⁺]=2.15. Add after appropriate water dilution, by Rake company manufacture catalyst for methanolMethod is prepared catalyst for methanol, makes catalyst A.

Embodiment 2

A kind of copper is Waste Catalyst during Methanol Synthesis, and it consists of (w%): CuO:61.45, ZnO:22.69, S:1.02, Al₂O₃：9.0，Fe(Fe₂O₃): 0.6, graphite: 2.0, C_xH_y: 0.2, water: 3.04. By this Waste Catalyst during Methanol Synthesis after remove impurity make use of physics methods, 900DEG C blowing air roasting 3 hours. Take the dead catalyst after 15g roasting, add 55mL30%HNO₃Solution. 40 DEG C of mechanical agitationReaction 1h, filters and obtains the transparent filtrate of navy blue. Add 2%NaHCO₃Solution regulates pH=3.5. Now in solution, Fe³⁺Content is0.1μg/L，[Cu²⁺]=108.65g/L，[Zn²⁺]=40.24g/L，[Cu²⁺]/[Zn²⁺]=2.70. Add after suitable quantity of water dilution,By existing method Kaolinite Preparation of Catalyst, make catalyst B.

Above sample is evaluated its activity with selective with fixed bed. With gas-chromatography TCD detector analytic sample, evaluation is urgedThe reactivity of agent. Use fid detector analytic sample, evaluate catalysts selective. And with industrial catalyst carry out rightRatio. The results are shown in Table 2.

Evaluation method: catalyst: 20-40 order, 3ml.

Reduction: 30%H₂/N₂Carry out temperature programmed reduction

Unstripped gas composition: CO16.65%, CO₂7.17%，N₂7.95%，H₂68.23%

Activity rating condition: 235 DEG C of reaction temperatures, pressure 5.0MPa, air speed 20000h^-1

Table 2: activity and selective evaluation result

Above data declaration, utilizing copper is the catalst for synthesis of methanol that Waste Catalyst during Methanol Synthesis reclaims preparation, selective and workIndustry is close with catalyst, active in industrial catalyst.

Claims

1. reclaiming copper is a method for Waste Catalyst during Methanol Synthesis, it is characterized in that: a kind of waste copper-series catylist, it consists of（w%）:CuO：60，ZnO：28，S：1.6，Al₂O₃：8.0，Fe₂O₃: 0.2, graphite: 2.0, C_xH_y: 0.2; By this dead catalystAfter remove impurity make use of physics methods at 900 DEG C of roasting 5h; Take the dead catalyst after 15g roasting, add 80ml20%HNO₃; Stir at 50 DEG CMix reaction 1 hour, filter and obtain the transparent filtrate of navy blue, add 4%NaHCO₃Solution, regulates pH=3.6; Now Fe in solution³⁺ContainAmount is 0.05 μ g/L, [Cu²⁺]=73.21g/L，[Zn²⁺]34.05g/L，[Cu²⁺]/[Zn²⁺]=2.15。

2. reclaiming copper is a method for Waste Catalyst during Methanol Synthesis, it is characterized in that: a kind of copper is Waste Catalyst during Methanol Synthesis, and it consists of（w%）：CuO：61.45，ZnO：22.69，S：1.02，Al₂O₃：9.0，Fe₂O₃: 0.6, graphite: 2.0, C_xH_y: 0.2, water: 3.04;By this Waste Catalyst during Methanol Synthesis after remove impurity make use of physics methods, 900 DEG C of blowing air roastings 3 hours; Take the dead catalyst after 15g roasting,Add 55mL30%HNO₃Solution; At 40 DEG C of mechanical agitation reaction 1h, filter and obtain the transparent filtrate of navy blue; Add 2%NaHCO₃Solution regulates pH=3.5; Now in solution, Fe³⁺Content is 0.1 μ g/L, [Cu²⁺]=108.65g/L，[Zn²⁺]=40.24g/L，[Cu²⁺]/[Zn²⁺]=2.70。