CN1203197C

CN1203197C - Method for preparing nickel and aluminium chemical product from catalyst refuse containing nickel and AL2O3

Info

Publication number: CN1203197C
Application number: CNB021330409A
Authority: CN
Inventors: 陈凯平
Original assignee: Individual
Current assignee: Individual
Priority date: 2002-09-26
Filing date: 2002-09-26
Publication date: 2005-05-25
Anticipated expiration: 2022-09-26
Also published as: CN1422967A

Abstract

The present invention relates to a method for recycling valuable metallic elements from catalyst waste slag, particularly to a method for recycling and reusing nickel and aluminium from catalyst waste slag which contains nickel and Al2O3. The catalyst waste slag is mixed with sodium hydroxide according to the molar ratio of NaOH to Al2O3 of 2 to 4:1. After 10 minutes to 10 hours of reaction at 300 to 800 DEG C, aluminium in the catalyst waste slag is firstly recycled and used by alkali fusion reaction, Al2O3 is further removed, and nickel in the catalyst waste slag is subsequently recycled and used by a conventional method. The recycling and using rate of aluminium is from 97 to 98%, and the recycling and using rate of nickel is also greatly increased to reach 90 to 99%. The present invention has the advantage of simple technical process, environmental protection and considerable economical and social benefits. The method of the present invention can be widely used in the treatment process of catalyst waste slag containing nickel and Al2O3 in petroleum industry, chemical industry, etc.

Description

From nickel, Al2O3Method for preparing nickel chemicals and aluminum chemicals from catalyst waste residues

(I) technical field

The invention relates to a method for recovering valuable metal elements from catalyst waste residue, in particular to a method for recovering valuable metal elements from nickel-containing Al₂O₃The method for preparing nickel chemicals and aluminum from the catalyst waste residue.

(II) technical background

Metallic nickel or nickel compounds with Al₂O₃Catalyst composed of carrier, simple substance or compound of nickel and other catalytic elements vanadium, molybdenum and the like, and Al₂O₃The catalyst composed of the carrier is widely applied to the petrochemical industry, and the catalyst loses activity after being used and is discarded. In recent years, acid-soluble or alkali-soluble methods have been used to recover nickel from catalyst waste residues to produce nickel chemicals such as nickel sulfate, nickel chloride, and nickel carbonate, but the recovery rate is low. For example, the hydrogenation catalyst for hydrogenation of benzene to cyclohexane is prepared from Al-Ni-C-Al₂O₃The content of nickel is about 20 percent, the recovery rate of chemicals for preparing nickel such as nickel sulfate and the like by recovering nickel by using a general acid-soluble oralkali-soluble method can only reach 70 to 80 percent, and 1 to 5 percent of nickel remained in waste residue cannot be recovered. A catalyst used in petroleum industry contains V13-14%, Mo 4%, Ni 4%, and Al as carrier₂O₃Vanadium is recovered from the catalyst waste residue, and the residue after molybdenum contains 5 to 6 percent of nickel, which can not be recovered at present.

Disclosure of the invention

The invention aims to solve the technical problem of providing a nickel-containing aluminum alloy₂O₃The method for recycling the nickel and the aluminum in the catalyst waste residue has the advantages that the recovery rate of the nickel recovered by the method is up to 90-99 percent, and meanwhile, the Al in the catalyst waste residue₂O₃Recovery of 97-98% was obtained.

The technical scheme adopted is as follows:

one kind of material containing Ni and Al₂O₃The method for preparing the nickel chemical and the aluminum chemical from the catalyst waste residue has the following principle:

in the presence of nickel and Al₂O₃In the catalyst slag of (3), Al₂O₃As its main component, Al₂O₃The amphoteric oxide can react with strong acid to generate aluminum salt, and can also react with strong base to generate aluminate. Al (Al)₂O₃Reactivity with strong acids or bases and Al₂O₃With respect to the crystal structure of (3), Al as a catalyst carrier₂O₃Generally, the catalyst is roasted at high temperature for a long time to generate crystals with compact structures, so that the reaction activity is greatly reduced, and the crystals cannot be completely dissolved by using common strong acid or strong base, so that the aluminum in the catalyst waste residue cannot be recovered, and more importantly, insoluble Al is obtained₂O₃The Al is removed first to achieve high nickel recovery rate because the Al and the nickel are remained in the catalyst slag together to influence the recovery rate of the nickel₂O₃I.e. first from the catalyst slagRecycling aluminum and removing Al therefrom₂O₃The nickel-containing (nickel is present as metallic nickel, nickel oxide, nickel sulfide, or the like) residue is recovered and reused by a conventional method.

Containing nickel and Al₂O₃The Al in the catalyst waste residue can be reacted with sodium hydroxide (or other alkali metal hydroxide) in a molten state, and the reaction temperature is controlled to be higher than the alkali melting temperature and lower than the volatilization temperature of nickel, so that the Al in the catalyst waste residue can be enabled₂O₃Completely reacting with alkali to form water-soluble sodium aluminate (or alkali metal aluminate), while nickel or nickel compound does not react with alkali and remains insoluble in water, thereby completely removing Al₂O₃The purpose of (1).

The reaction equation is as follows:

one kind of material containing Ni and Al₂O₃The method for recycling nickel and aluminum from the catalyst waste residue sequentially comprises the following steps:

1. taking nickel and Al₂O₃The mixing ratio of the waste catalyst residue and the caustic soda is satisfied, so that NaOH and Al are mixed at the beginning of the reaction₂O₃The molar ratio of (A) to (B) is 2-4: 1. The molar ratio is preferably from 2.4 to 3: 1.

2. Mixing the catalyst waste residue and caustic soda, heating the mixture in a muffle furnace in a crucible made of nickel or iron, or heating the mixture in a box-type or tunnel-type kiln by high-temperature hot air to 800 ℃ for 300-: 。

3. dissolving the reacted blocks in water to prepare a sodium aluminate solution with the concentration of 120-300 g/l.

4. Filtering or naturally settling, centrifugally settling and other solid-liquid separation treatment is carried out on the sodium aluminate solution containing insoluble nickel residues to obtain nickel residues and NaAlO₂And (3) solution.

5. And washing and drying the nickel-containing residue to obtain nickel-rich residue.

NaAlO after solid-liquid separation₂Evaporating the solution to prepare solid sodium aluminate. The method can also be used for preparing products such as aluminum hydroxide, aluminum oxide and the like by a seed precipitation method or a carbon precipitation method, and simultaneously preparing a byproduct sodium hydroxide or sodium carbonate.

According to the removal of Al₂O₃The different existing states of nickel in the nickel-rich residue: the metal nickel, nickel sulfide or nickel oxide, etc. are dissolved in sulfuric acid and nitric acid or sulfuric acid alone according to conventional method, and the reaction equation is:

if the nickel existing in the nickel-rich waste residue is metallic nickel, the process for preparing the nickel sulfate is as follows: per kilogramAdding 5kg of 33-35% sulfuric acid into nickel, heating to 80 ℃ in an enamel reaction kettle, dropwise adding 200-300g of 50% concentrated nitric acid, reacting for 4 hours to obtain a crude nickel sulfate solution, neutralizing with a lime milk solution until the pH value is 4.5-5.0, and precipitating and separating out aluminum hydroxide. Separating solid and liquid by natural settling or filtering, removing precipitate, adjusting pH of the clear liquid to 2 with sulfuric acid, adding 27.5% H₂O₂Solution of Fe in the clear solution²⁺Complete conversion of impurities into Fe³⁺Heating to 80 deg.C, slowly adding nickel carbonate, adjusting pH to 4.0-5.0, and then Fe (OH)₃And CaCO₃Precipitating, reacting for 0.5 hr, cooling, standing for 5 hr, filtering to obtain clear solution with pH of 2-3, heating and concentrating until the specific gravity of the solution is 1.53-1.63g/cm³Naturally cooling and crystallizing, removing the non-crystallized liquid by a centrifugal machine, drying in a sealed container filled with silica gel for 10 hours, and packaging to obtain the finished product of nickel sulfate crystal.

If the nickel in the nickel-rich residue is nickel sulfide or nickel oxide, the crude nickel sulfate solution can be prepared according to the requirement of the reaction equation, and then the impurities such as aluminum, iron and the like are removed by the method to prepare the refined nickel sulfate.

The invention has the following advantages and positive effects:

1. NaAlO obtained by solid-liquid separation₂The solution can be directly used as a sodiumaluminate solution product, can also be evaporated to prepare a solid sodium aluminate product, and can also be used for preparing products such as aluminum hydroxide, aluminum oxide and the like by a seed precipitation method or a carbon precipitation method, and simultaneously obtaining a byproduct sodium hydroxide or sodium carbonate. Realizes the purpose of removing nickel and Al₂O₃The aluminum is recycled from the catalyst waste residue, and the recovery rate can reach 97-98%.

2. The invention recovers the aluminum element in the catalyst waste residue firstly, namely, removes Al firstly₂O₃The method creates favorable conditions for the subsequent recycling of nickel, makes the recycling of nickel in the catalyst waste residue containing 5 to 6 percent of nickel after extracting useful elements such as vanadium, molybdenum and the like possible, greatly improves the recovery rate of nickel elements and achieves the recovery rate of 90 to 99 percent.

3. The method is simple and convenient, is easy to operate, is beneficial to environmental protection, and has considerable economic and social benefits.

4. The nickel-containing residue obtained after solid-liquid separation is washed and dried to obtain nickel-rich residue, which can be directly sold as a nickel-rich raw material or further processed into nickel chemicals such as nickel sulfate, nickel carbonate, nickel chloride, nickel acetate and the like.

(IV) detailed description of the preferred embodiments

Example one

The main raw materials are as follows: the catalyst waste residue contains 5 percent of nickel and 90 percent of Al according to weight percentage₂O₃(ii) a Caustic soda solution, concentration 45%.

Mixing 100g of catalyst waste residue and 200g of caustic soda solution in an iron dissolving vessel, heating and evaporating to be thick paste, putting the mixture into a nickel crucible, heating the mixture to 450 ℃ in a muffle furnace at the final temperature of 200 ℃, drying the mixture for 3 hours at the temperature, putting the reactant which is fused into blocks into 5 liters of water, dissolving the reactant, and naturally settling the reactant, wherein the upper layer is transparent colorless clear liquid, and the lower layer is black brown sludge. The upper layer of clear liquid is sodium aluminate solution with the concentration of 200g/l and the recovery rate of aluminum is 97-98%; washing the lower layer of sludge for 5 times, and drying the filtered filter residue in an oven at 100 ℃ for 5 hours to obtain 11g of black brown residue containing 45% of nickel.

Putting the dark brown residue into a three-necked flask, and adding 315g of 35% H₂SO₄Heating the solution to 80 deg.C, and adding 65g of HNO with concentration of 50%₃Adding dropwise the solution within 30-60 min, reacting for 3 hr, cooling to room temperature, adding lime milk solution, adjusting pH to 4.5, filtering, removing precipitate, and adding H₂SO₄The pH of the filtrate was adjusted to 2 and 21ml of 27.5% H was added₂O₂Solution of Fe²⁺To Fe³⁺Heating to 80 deg.C, slowly adding nickel carbonate while stirring to pH 4.0, cooling, standing for 5 hr, filtering with H₂SO₄Adjusting pH of the filtrate to 2, heating and concentrating until the specific gravity of the solution is 1.55g/cm³Naturally cooling and crystallizing to obtain sulfur210g of nickel acid crystals were obtained, and the recovery rate was 97%.

Example two

The process of the raw materials and other conditions are basically the same as that of the first embodiment, the alkali-melting reaction temperature in the muffle furnace is changed to 800 ℃, and the reaction time is changed to 15 minutes. As a result: the recovery rate of aluminum is 97-98%, and the recovery rate of nickel is 92%.

EXAMPLE III

The main raw materials are as follows: the nickel-containing catalyst residue after extracting useful elements such as vanadium, molybdenum and the like contains 34 percent of water and 60 percent of Al according to weight percentage₂O₃3.5% nickel.

The catalyst residue 7kg, and 96% solid caustic soda 4.5kg, fully mixed, placed into iron pan, dried in 550 ℃ high temperature hot air box type dryer for 3 hours, taken out and observed, the block has been melted into a block, the block is put into 30 liters of water to dissolve, insoluble substances precipitate, filtration, water washing, drying, 0.5kg of nickel-rich residue is obtained.

The rest of the treatment process is the same as the first example, and sodium metaaluminate, aluminum hydroxide, aluminum oxide and other aluminum chemicals and 1.09kg of nickel sulfate are prepared. As a result: the recovery rate of aluminum is 97-98%, and the recovery rate of nickel is 94%.

Claims

1. From nickel, Al₂O₃The method for preparing the nickel chemical and the aluminum chemical from the catalyst waste residue is characterized in that the aluminum in the catalyst waste residue is recycled firstly by alkali fusion reaction, and the Al in the catalyst waste residue is removed₂O₃And then recycling the nickel in the catalyst waste residue, wherein the specific method sequentially comprises the following steps:

a. taking nickel and Al₂O₃The weight ratio of the waste residue of the catalyst to the caustic soda is that NaOH and Al are in the beginning of the reaction₂O₃The molar ratio of (A) to (B) is 2-4: 1;

b. mixing the obtained catalyst waste residue with caustic soda, performing alkali fusion reaction in a crucible made of nickel or iron in a muffle furnace, namely heating to 800 ℃ in an alkali fusion reaction container, performing alkali fusion reaction for 10 minutes to 10 hours, and obtaining a reaction formulaThe program is as follows: ；

c. dissolving the reacted lumps in water to prepare a sodium aluminate solution with the concentration of 120-;

d. filtering or naturally settling and centrifugally settling the sodium aluminate solution containing insoluble nickel residue to separate solid from liquid to obtain nickel residue and NaAlO₂A solution;

e. NaAlO after solid-liquid separation₂Evaporating the solution to prepare sodium aluminate, or preparing aluminum hydroxide and aluminum oxide products by a seed precipitation method or a carbon precipitation method, and simultaneously preparing a byproduct sodium hydroxide or sodium carbonate;

f. washing and drying the nickel-containing residue to obtain a nickel-rich raw material;

g. according to the removal of Al₂O₃The different existing states of nickel in the nickel-rich residue: the metal nickel, nickel sulfide or nickel oxide, the nickel-rich residue is dissolved by sulfuric acid and nitric acid or sulfuric acid alone according to the conventional method, and the reaction equations are respectively:

2. the alloy of claim 1, comprising nickel, Al₂O₃The method for preparing nickel chemicals and aluminum chemicals from catalyst waste residue is characterized in that NaOH and Al are recycled when the alkali fusion reaction of aluminum is started₂O₃The molar ratio of (1) to (2.4-3) to (1), the reaction temperature is 400-600 ℃, and the reaction duration is 1-1.5 hours.

3. The alloy of claim 1, comprising nickel, Al₂O₃Preparation of nickel from catalyst waste residueA method for producing chemicals and aluminum chemicals, characterized in that the alkali fusion reaction is carried out in a box-type or tunnel-type kiln using high-temperature hot air.