阅读说明：本技术 一种加氢催化剂的制法 (Preparation method of hydrogenation catalyst ) 是由 吕振辉 朱慧红 杨涛 金浩 刘璐 杨光 于 2019-09-17 设计创作，主要内容包括：本发明公开了一种加氢催化剂的制备方法,包括如下内容：(1)将含活性组分钼、镍的废加氢催化剂抽提除油、焙烧除碳、粉碎和筛分；(2)将筛分后的废加氢催化剂粉末与碱混合,然后焙烧处理和热水浸渍处理,然后过滤,得滤液I和固体残渣；(3)将步骤(2)的固体残渣焙烧,然后与酸混合反应,过滤,得到滤液II；(4)将滤液I和滤液II首先调节pH值2.0～3.0,晶化,再调节pH值10.0～11.0,晶化,然后进行摆动成胶,老化,得到催化剂前驱体；(5)将催化剂前驱体挤条可塑性载体,干燥、焙烧得到加氢催化剂。本方法过程简单,金属利用率高,处理成本低,适用于废催化剂的回收利用。(The invention discloses a preparation method of a hydrogenation catalyst, which comprises the following steps: (1) extracting the waste hydrogenation catalyst containing active components of molybdenum and nickel to remove oil, roasting to remove carbon, crushing and screening; (2) mixing the screened waste hydrogenation catalyst powder with alkali, then carrying out roasting treatment and hot water impregnation treatment, and then filtering to obtain filtrate I and solid residue; (3) roasting the solid residue obtained in the step (2), mixing the solid residue with acid for reaction, and filtering to obtain a filtrate II; (4) firstly adjusting the pH value of the filtrate I and the filtrate II to 2.0-3.0, crystallizing, adjusting the pH value to 10.0-11.0, crystallizing, then swinging to form colloid, and aging to obtain a catalyst precursor; (5) extruding a catalyst precursor into a plastic carrier, drying and roasting to obtain the hydrogenation catalyst. The method has simple process, high metal utilization rate and low treatment cost, and is suitable for recycling the waste catalyst.)

1. A preparation method of a hydrogenation catalyst is characterized by comprising the following steps: (1) extracting the waste hydrogenation catalyst containing active components of molybdenum and nickel to remove oil, roasting to remove carbon, crushing and screening; wherein the hydrogenation catalyst takes alumina or modified alumina as a carrier; (2) mixing the screened waste hydrogenation catalyst powder with alkali, then carrying out roasting treatment and hot water impregnation treatment, and then filtering to obtain filtrate I and solid residue; (3) roasting the solid residue obtained in the step (2), mixing the solid residue with acid, reacting and dissolving the mixture for a period of time, and filtering the mixture to obtain filtrate II; (4) filtrate I and filtrate II were subjected to the following process under stirring: firstly, adjusting the pH value to be 2.0-3.0, crystallizing for 15-30 min, adjusting the pH value to be 10.0-11.0, crystallizing for 5-10 min, then carrying out pH value swing neutralization and gelling, after gelling, adjusting the pH value to be 7.0-9.0, aging for a period of time, then filtering, and drying to obtain a catalyst precursor; (5) extruding the catalyst precursor obtained in the step (4) into a plastic carrier, and drying and roasting the carrier to obtain the hydrogenation catalyst.

2. The method of claim 1, wherein: step (1), taking the weight of the waste hydrogenation catalyst as a reference, 70-90 wt% of catalyst solid and 10-30 wt% of petroleum fraction; based on the weight of the waste hydrogenation catalyst after oil extraction and removal, the weight of nickel oxide is 2-10 wt%, and the weight of molybdenum oxide is 8-25 wt%.

3. The method of claim 1, wherein: in the step (2), the alkali is sodium hydroxide and/or sodium carbonate; the molar ratio of the alkali to the waste hydrogenation catalyst powder is 2.0-5.0 in terms of metal oxide: 1.

4. the method of claim 1, wherein: the roasting treatment conditions in the step (2) are as follows: the temperature is 500-800 ℃, and the time is 0.5-4.0 h.

5. The method of claim 1, wherein: the hot water dipping treatment conditions in the step (2) are as follows: the temperature of the leaching water is 50-100 ℃, and the leaching time is 30-120 min; the liquid-solid mass ratio is 2: 1-10: 1; the leaching rate of molybdenum oxide is 90-98%, and the leaching rate of aluminum oxide is 35-55%.

6. The method of claim 1, wherein: in the step (3), the acid is nitric acid, sulfuric acid or hydrochloric acid.

7. The method of claim 1, wherein: roasting the solid residue in the step (3) at the temperature of 200-800 ℃; the roasting time is 3-10 h.

8. The method of claim 1, wherein: the molar ratio of the acid to the solid residue in the step (3) is 2.0-4.0 in terms of metal oxides: 1, preferably 2.5 to 3.5: 1.

9. the method of claim 1, wherein: the reaction time in the step (3) is 0.5-3.0 h, and the dissolving temperature is 80-150 ℃; the dissolution rate of molybdenum and/or nickel is 90-98%, and the dissolution rate of alumina is 90-98%.

10. The method of claim 1, wherein: in the step (4), the mass concentration of molybdenum in the filtrate I is 15-50 g/100mL based on molybdenum oxide, and the mass concentration of aluminum is 10-20 g/100mL based on aluminum oxide; in the filtrate II, the total mass concentration of nickel and/or cobalt is 5-10 g/100mL calculated as oxide, and the mass concentration of aluminum is 5-10 g/100mL calculated as alumina.

11. The method of claim 1, wherein: and (4) the temperature for neutralizing and gelatinizing the pH value in the step (4) is 50-100 ℃, the pH value swing range is that the acid pH value is 2.0-3.0, the alkaline pH value is 10.0-11.0, and the swing frequency is 3-8 times.

12. The method of claim 1, wherein: and (4) aging at the pH value of 7.0-9.0 and the temperature of 50-100 ℃ for 0.5-2.5 h.

13. The method of claim 1, wherein: in the step (5), the roasting temperature is 300-550 ℃, preferably 300-400 ℃, and the roasting time is 2.0-5.0 h.

Technical Field

The invention relates to a preparation method of a hydrogenation catalyst, in particular to a method for preparing the hydrogenation catalyst by recycling a waste catalyst.

Background

The molybdenum-nickel active metal content of the residual oil hydrogenation catalyst is relatively low, the metal recovery problem is mainly considered by catalyst recovery enterprises at present, and the carrier utilization rate is too low for alumina carriers which are basically used as waste residues for cement or ceramic enterprises. The recovery and reuse of active metals and alumina is an important direction of the current catalyst research.

CN201611011637.6 discloses a method for recycling hydrotreating catalyst, which comprises the following steps: (1) extracting, roasting and crushing the molybdenum-nickel system waste catalyst; (2) mixing the crushed catalyst powder with alkali, and then carrying out microwave treatment; (3) adding an acid solution into the molybdate solution obtained in the step (2) to obtain molybdic acid; (4) crushing the alumina filter residue obtained in the step (2), mixing with alkali again, roasting, dipping in hot water, and filtering to obtain an aluminate solution and a nickel oxide solid; (5) introducing carbon dioxide into the aluminate solution obtained in the step (4), preparing pseudo-boehmite by using a carbonization method, mixing the pseudo-boehmite with an adhesive, and preparing a carrier by molding, drying and roasting; (6) adding acid into the nickel oxide obtained in the step (4) to prepare a nickel solution, and adding carbonate to prepare basic nickel carbonate; (7) and (4) preparing molybdic acid in the step (3) and the basic nickel carbonate in the step (6) into a molybdenum-nickel-phosphorus solution, then impregnating the molybdenum-nickel-phosphorus solution on the carrier in the step (5), and drying and roasting the molybdenum-nickel-phosphorus solution to prepare the catalyst. The method is particularly suitable for recovering the molybdenum-nickel spent catalyst to prepare a new catalyst, but the process is complex.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a method for preparing a hydrogenation catalyst by recovering a waste catalyst. The method has the characteristics of simple preparation process, high metal utilization rate, low treatment cost and the like.

The preparation method of the hydrogenation catalyst comprises the following steps:

(1) extracting the waste hydrogenation catalyst containing active components of molybdenum and nickel to remove oil, roasting to remove carbon, crushing and screening; wherein the hydrogenation catalyst takes alumina or modified alumina as a carrier;

(2) mixing the screened waste hydrogenation catalyst powder with alkali, then carrying out roasting treatment and hot water impregnation treatment, and then filtering to obtain filtrate I and solid residue;

(3) roasting the solid residue obtained in the step (2), mixing the solid residue with acid according to a certain proportion, reacting for a period of time under the condition of stirring, and filtering to obtain filtrate II;

(4) filtrate I and filtrate II were subjected to the following process under stirring: firstly, adjusting the pH value to be 2.0-3.0, crystallizing for 15-30 min, adjusting the pH value to be 10.0-11.0, crystallizing for 5-10 min, then carrying out pH value swing neutralization and gelling, after swinging for a certain number of times and gelling, adjusting the pH value to be 7.0-9.0 after gelling, aging for a period of time, filtering, and drying to obtain a catalyst precursor;

(5) extruding the catalyst precursor obtained in the step (4) into a plastic carrier, and drying and roasting the carrier to obtain the hydrogenation catalyst.

In the method, in the step (1), based on the weight of the waste hydrogenation catalyst, 70-90 wt% of catalyst solid and 10-30 wt% of petroleum fraction are used; based on the weight of the waste hydrogenation catalyst after oil extraction and removal, the weight of nickel oxide is 2-10 wt%, and the weight of molybdenum oxide is 8-25 wt%. The organic solvent adopted for extraction and oil removal is toluene, petroleum ether, ethanol and the like, and the extraction temperature is 80-110 ℃; the roasting decarbonization temperature is 500-700 ℃, preferably 600-650 ℃, and the time is 3-5 hours; after crushing and screening, the granularity is 200-400 meshes, preferably 300-400 meshes.

In the method of the present invention, the alkali in the step (2) may be sodium hydroxide and/or sodium carbonate, preferably sodium carbonate; the molar ratio of the alkali to the waste hydrogenation catalyst powder is 2.0-5.0 in terms of metal oxide: 1, preferably 2.0 to 3.5: 1.

in the method of the invention, the roasting treatment conditions in the step (2) are as follows: the temperature is 500-800 ℃, preferably 550-750 ℃, and the time is 0.5-4.0 h, preferably 0.5-3.0 h; the roasting atmosphere is one or more of air, nitrogen and the like.

In the method of the invention, the hot water dipping treatment conditions in the step (2) are as follows: the temperature of the leaching water is 50-100 ℃, and preferably 80-100 ℃; the leaching time is 30-120 min, preferably 30-90 min; the liquid-solid mass ratio is 2: 1-10: 1, preferably 4: 1-8: 1; the leaching rate of the molybdenum oxide is 90-98%, preferably 95-98%, and the leaching rate of the aluminum oxide is 35-55%, preferably 45-50%. The leaching rate was calculated as the ratio of the amount of oxide contained in the solid before leaching to the amount of oxide contained after leaching.

In the method of the present invention, the acid in step (3) is nitric acid, sulfuric acid or hydrochloric acid, preferably sulfuric acid, and the acid concentration is adjusted according to the kind of the acid and the need.

In the method, the roasting temperature of the solid residue in the step (3) is 200-800 ℃, and preferably 500-800 ℃; the roasting time is 3-10 h; the molar ratio of the acid to the solid residue is 2.0-4.0 in terms of metal oxides: 1, preferably 2.5 to 3.5: 1. the reaction time is 0.5-3.0 h, preferably 1.0-3.0 h. The dissolving temperature is 80-150 ℃, and preferably 100-120 ℃. The dissolution rate of molybdenum and/or nickel is 90-98%, preferably 95-95%, and the dissolution rate of alumina is 90-98%, preferably 90-95%.

In the method, the mass concentration of molybdenum in the filtrate I in the step (4) is 15-50 g/100mL calculated as molybdenum oxide, and the mass concentration of aluminum is 10-20 g/100mL calculated as aluminum oxide; in the filtrate II, the total mass concentration of nickel and/or cobalt is 5-10 g/100mL calculated as oxide, and the mass concentration of aluminum is 5-10 g/100mL calculated as alumina. The concentration of the solution can be controlled and adjusted by heating and distilling or adding water for dilution.

In the method, the stirring speed in the step (4) is 20-100 rad/min, preferably 20-50 rad/min; the temperature for neutralizing and gelatinizing the pH value in a swinging way is 50-100 ℃, and the optimal temperature is 70-100 ℃; the pH value swing range is that the acid pH value is 2.0-3.0, the alkaline pH value is 10.0-11.0, the swing frequency is 3-8 times, and 3-5 times is preferred; the aging pH value is 7.0-9.0, the aging temperature is 50-100 ℃, the aging temperature is preferably 70-100 ℃, and the aging time is 0.5-2.5 h, preferably 1.0-2.0 h.

In the method, in the step (5), the drying temperature is 100-200 ℃, preferably 120-150 ℃, the roasting temperature is 300-550 ℃, preferably 300-400 ℃, and the roasting time is 2.0-5.0 h, preferably 2.0-4.0 h.

Compared with the prior art, the preparation method of the hydrogenation catalyst provided by the invention has the following advantages: the method dissolves and removes the molybdenum and part of the alumina in the waste catalyst in the step (2), dissolves and removes the nickel and part of the alumina in the solid residue by acidification in the step (3), can recycle the required active metal and the alumina to the maximum extent by the process, and improves the recovery rate. The active metal salt is precipitated under the acidic pH value condition in the step (4), the active metal salt with strong polarity and small particles is used as a seed crystal, the seed crystal has higher directional speed and is easy to form crystal form precipitates or colloidal particles with a crystal structure, on one hand, the crystals grow directionally, the crystal crystallinity is high, the crystals are more complete, on the other hand, the phase inversion temperature of a precursor is reduced, the roasting temperature of the catalyst can be obviously reduced, the strength of the catalyst product can be improved at low temperature, and simultaneously, the low-temperature roasting reduces the phenomena of inactive nickel-aluminum spinel and active metal agglomeration, so that the interaction between the active metal and a carrier and the active metal is weakened, the catalyst is easier to be sulfurized into a high-activity II-type active phase, the activity is higher, and the activity is higher. The hydrogenation catalyst prepared by the waste catalyst can directly recover active metal and alumina in the waste catalyst, and is an environment-friendly catalyst preparation method; the utilization rate of active metal and alumina can be obviously improved, the recycling economy of the catalyst is realized, the environmental condition is improved, and the production cost of the catalyst is greatly reduced.

Detailed Description

In the method, the specific surface area and the pore volume are measured by adopting a low-temperature liquid nitrogen adsorption method; analyzing the surface dispersity of the active metal in the catalyst by using an XPS spectrometer; analyzing the concentration of the metal in the solution by adopting a fluorescence spectrum method; the contents of metal oxides in the catalyst and solid residues were analyzed by XRF method.

The preparation process of the hydrogenation catalyst of the present invention is described in more detail below by way of specific examples. The examples are merely illustrative of specific embodiments of the process of the present invention and do not limit the scope of the invention.

Extracting and deoiling a molybdenum-nickel catalyst subjected to industrial operation, roasting, and screening, wherein the roasting temperature is 600 ℃; weighing 200g of catalyst, crushing to 300 meshes, uniformly mixing with 400g of sodium carbonate, and roasting at 600 ℃ for 4.0 h; leaching with hot water of 300g at 90 deg.C, filtering, leaching molybdenum oxide at 97% and alumina at 49% to obtain alkaline solution and solid residue of about 250 g; adding 200mL of 50% concentrated sulfuric acid into the solid residue containing nickel and aluminum, stirring and reacting at 100 ℃ for 2.0h, and filtering to obtain an acidic solution. Finally, adding water to adjust the concentration of molybdenum oxide in the alkaline solution to be 20g/100mL and the concentration of aluminum oxide to be 15g/100 mL; the concentration of nickel oxide in the acidic solution was 7g/100mL and the concentration of alumina was 8g/100 mL.

5L of purified water is added into the gelling tank, and the mixture is heated to 70 ℃. Adding a certain amount of the alkaline solution into a neutralization and gelling tank, adding sulfuric acid to adjust the pH value to be 2.0, precipitating a small amount of molybdenum oxide and aluminum oxide to be used as seed crystals and crystallizing for 20min, then adding the alkaline solution to adjust the pH value to be 10.0, and stabilizing for 5 min; and then adjusting the pH value to 2.0 by using the acidic solution, stabilizing for 5min, adjusting the pH value to 10.0 by using the alkaline solution, repeating for 4 times, adjusting the pH value to 8.0, aging at the temperature of 70 ℃, aging for 1.0h, filtering, and drying to obtain the required catalyst precursor.

And mixing the catalyst precursor with an adhesive, molding, drying at 120 ℃, and roasting at 350 ℃ for 3 hours to obtain the catalyst A.