阅读说明：本技术 一种重石脑油脱硫剂及其制备方法 (Heavy naphtha desulfurizer and preparation method thereof ) 是由 李选志 曹晓玲 潘喜强 于 2020-12-19 设计创作，主要内容包括：本发明公开了一种重石脑油脱硫剂,由以下质量百分含量的成分组成：活性氧化铝10％～50％,分子筛10％～50％,复合金属氧化物30％～60％；本发明还公开了一种重石脑油脱硫剂的制备方法,将复合金属氧化物对应的硝酸盐溶液滴加到铵盐溶液中反应,干燥后焙烧得到复合金属氧化物,再与载体原料、粘结剂和水混匀捏合成型,再依次经干燥和焙烧得到重石脑油脱硫剂。本发明的重石脑油脱硫剂采用复合金属氧化物结合采用活性氧化铝和分子筛作为载体,使得活性组分复合金属氧化物充分分散在载体中,提高了重石脑油脱硫剂的净化度和硫容；本发明采用化学沉淀法并以碳酸铵或碳酸氢铵为沉淀剂,避免引入杂质离子,便于工业生产。(The invention discloses a heavy naphtha desulfurizer which comprises the following components in percentage by mass: 10 to 50 percent of activated alumina, 10 to 50 percent of molecular sieve and 30 to 60 percent of composite metal oxide; the invention also discloses a preparation method of the heavy naphtha desulfurizer, which comprises the steps of dropwise adding a nitrate solution corresponding to the composite metal oxide into the ammonium salt solution for reaction, drying, roasting to obtain the composite metal oxide, uniformly mixing the composite metal oxide with the carrier raw material, the binder and water, kneading and forming, and drying and roasting in sequence to obtain the heavy naphtha desulfurizer. The heavy naphtha desulfurizer of the invention adopts composite metal oxide combined with active alumina and molecular sieve as carriers, so that the active component composite metal oxide is fully dispersed in the carriers, and the purification degree and the sulfur capacity of the heavy naphtha desulfurizer are improved; the invention adopts a chemical precipitation method and takes ammonium carbonate or ammonium bicarbonate as a precipitator, thereby avoiding the introduction of impurity ions and being convenient for industrial production.)

1. The heavy naphtha desulfurizer is characterized by comprising the following components in percentage by mass: 10 to 50 percent of activated alumina, 10 to 50 percent of molecular sieve and 30 to 60 percent of composite metal oxide.

2. The heavy naphtha desulfurizer as claimed in claim 1, wherein the activated alumina is γ -Al₂O₃Or AlOOH. nH₂O。

3. The heavy naphtha desulfurization agent according to claim 1, wherein the molecular sieve is at least one of ZSM-5, Y type and 13X molecular sieve.

4. The heavy naphtha desulfurizing agent according to claim 1, wherein the metal elements of said complex metal oxide include two or three of copper, zinc, magnesium, calcium, nickel, iron and manganese.

5. A process for preparing a heavy naphtha desulfurization agent as set forth in any one of claims 1 to 4, which comprises the steps of:

dissolving nitrates of two or three metal elements of copper, zinc, magnesium, calcium, nickel, iron and manganese in deionized water, and then heating to 40-70 ℃ to obtain a solution A;

dissolving ammonium salt in deionized water, and heating to 30-50 ℃ to obtain a solution B;

step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 7-10, then heating to 70-90 ℃, standing for 30-120 min, and carrying out suction filtration and washing on the obtained precipitate to obtain a filter cake;

step four, drying the filter cake obtained in the step three, and then roasting to obtain a composite metal oxide;

and step five, adding the composite metal oxide obtained in the step four, active alumina powder, molecular sieve raw powder, dry powder of an organic binder and water into a mixer, uniformly mixing and kneading to obtain a strip material to be extruded, then placing the strip material to be extruded into a forming machine for strip extrusion forming to obtain a strip material, and then drying and roasting the strip material in sequence to obtain the heavy naphtha desulfurizer.

6. The method according to claim 5, wherein the total molar concentration of metal ions in the solution A in the first step is 0.1mol/L^-1～1.0mol/L^-1。

7. The method according to claim 5, wherein the ammonium salt in the second step is ammonium carbonate or ammonium bicarbonate, and the mass concentration of the solution B is 10-15%.

8. The method according to claim 5, wherein the drying temperature in the fourth step and the drying temperature in the fifth step are both 80-120 ℃ and the drying time is 8-12 h, and the roasting temperature is 300-500 ℃ and the drying time is 4-6 h.

9. The method as claimed in claim 5, wherein the organic binder in step five is carboxymethyl cellulose, sesbania powder or tonka bean powder, and the mass of the organic binder is 3% of the total mass of the composite metal oxide and the dry powder of the activated alumina powder, the molecular sieve raw powder and the organic binder.

10. The method according to claim 5, wherein in the fifth step, the mixer is a kneader or a grinder, and the mixing time is 20min to 30 min; the forming machine is a screw rod extruding machine or an oil pressure extruding machine.

Technical Field

The invention belongs to the field of petrochemical catalytic purificant, and particularly relates to a heavy naphtha desulfurizer and a preparation method thereof.

Background

Naphtha is a product of primary or secondary processing of crude oil or other oils by refinery enterprises, and can be classified into light naphtha and heavy naphtha according to the difference of distillation cut points. The heavy naphtha has high potential aromatic hydrocarbon content and low nitrogen and sulfur content, so that the heavy naphtha is the most important raw material for producing high-octane gasoline and aromatic hydrocarbon. In recent years, the heavy naphtha processing equipment has become larger and larger, so that the raw material demand is lowThe number of the supply and demand contradictions is increasing. The refining enterprises carry out hydrocracking treatment on heavy diesel oil, wax oil or mixed diesel wax oil, and simultaneously improve the cut point of heavy naphtha so as to obtain more heavy naphtha raw materials. In the production process of the heavy naphtha, the sulfur content in the heavy naphtha is seriously exceeded due to the heavy raw material and the complication of the sulfur form in the raw material. The analysis shows that the total sulfur content in the heavy naphtha is about 3-5 mug g^-1In which H is₂The S content accounts for about 70 percent of the total sulfur, and the rest is the mercaptan organic sulfur. The literature data show that when heavy naphtha is used as a raw material for catalytic reforming, the sulfur content in the heavy naphtha is 1. mu.g.g^-1When the activity of the reforming catalyst is affected, the liquid yield and hydrogen yield above C5 decrease. When the sulfur content in the heavy naphtha was 1.5. mu.g g^-1During the process, the activity of the reforming catalyst is reduced by about 20%, the service cycle of the catalyst is shortened, and the sulfur content in the liquid product exceeds the standard. Similarly, heavy naphthas containing excess sulfide can also poison the isomerization catalyst, resulting in permanent catalyst deactivation. At present, researchers and the industry generally believe that when the sulfur content of heavy naphtha is below 0.5 μ g^-1In the meantime, the requirement for reprocessing the raw material can be satisfied, and thus, the heavy naphtha desulfurization technology is regarded as important.

The fixed bed dry desulfurization technology is also applied to the heavy naphtha desulfurization process due to the advantages of simple flow, convenient application and the like. In the 'application of heavy naphtha desulfurization technology', such as strong light irradiation, ZnO desulfurizer is adopted to remove sulfide in heavy naphtha; the results of experiments on the removal of hydrogen sulfide from naphtha by an iron oxide desulfurizer are introduced in 'evaluation of use effect of naphtha desulfurizer'; benyan and the like performed research on regeneration performance of desulfurization adsorbent for heavy naphtha by medium-pressure hydrogenation by using clay/active carbon as a desulfurizing agent. In the technology, the ZnO desulfurizer is suitable for being used at high temperature, and when the ZnO desulfurizer is used at low temperature, the sulfur capacity is low, and the service cycle of the desulfurizer is short; the iron oxide desulfurizer has low desulfurization precision, can not meet the requirement of raw material purification degree, is easy to harden and argillize when meeting water, and influences the service life. Although the activated carbon adsorbent has good removal capacity for sulfur in heavy naphtha, the sulfur capacity is low, frequent regeneration is needed, and the process is complex.

In the prior art, various metal oxide carriers are also used as a naphtha desulfurizer on alumina, for example, chinese patent CN111410986A describes a preparation method of a naphtha fine desulfurizer, the desulfurizer uses copper nitrate, zinc nitrate, aluminum nitrate and nickel nitrate as raw materials to prepare a solution, then sodium carbonate is added to neutralize and precipitate, and after neutralization is finished, the precipitate is filtered, washed, dried and roasted to obtain a heavy naphtha desulfurizer. The method has the following problems: the nitrate solution uses sodium carbonate as a precipitator in the neutralization process, so that undesirable Na is introduced in the preparation process of the desulfurizer⁺A large amount of water is used for washing and removing in the subsequent process, so that water resources are wasted; in the using process of the industrial desulfurizer, powder is prepared into particles with certain shapes and then is filled into a reactor to reduce the resistance of the reactor, and the forming of the powder has great influence on the pore structure and the activity of the desulfurizer. The desulfurizer powder prepared by the method is not subjected to molding treatment, and has no industrial application value.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a heavy naphtha desulfurizer aiming at the defects of the prior art. According to the heavy naphtha desulfurizer, the uniform mixing degree of each metal oxide in the active components is improved by adopting the composite metal oxide, and the active alumina and the molecular sieve are combined to be adopted as carriers, so that the composite metal oxide is fully dispersed in the active alumina and the molecular sieve, the dispersion degree of the active components is improved, more reactive active sites are provided, and the purification degree and the sulfur capacity of the heavy naphtha desulfurizer are improved.

In order to solve the technical problems, the invention adopts the technical scheme that: the heavy naphtha desulfurizer is characterized by comprising the following components in percentage by mass: 10 to 50 percent of activated alumina, 10 to 50 percent of molecular sieve and 30 to 60 percent of composite metal oxide.

Compared with the desulfurizer consisting of one oxide or two oxide powders and alumina powder in the prior art, the heavy naphtha desulfurizer of the invention consists of carrier active alumina, a molecular sieve and active component composite metal oxide, the uniform mixing degree of each metal oxide in the active component is improved by adopting the composite metal oxide, high specific surface area is provided by combining the active alumina, and rich pore channels and proper pore diameter are provided by adopting the molecular sieve, so that the composite metal oxide is fully dispersed in the active alumina and the molecular sieve, the dispersion degree of the active component is improved, more reactive active sites are provided, the desulfurization performance of the heavy naphtha desulfurizer is improved, and the purification degree and the sulfur capacity of the heavy naphtha desulfurizer are improved.

The heavy naphtha desulfurizer is characterized in that the active alumina is gamma-Al₂O₃Or AlOOH. nH₂And O. The optimized active alumina has large specific surface area and high pore volume, is more beneficial to the diffusion and reaction of liquid phase material heavy naphtha, and realizes better desulfurization effect.

The heavy naphtha desulfurizer is characterized in that the molecular sieve is at least one of ZSM-5, Y-type and 13X molecular sieves. The optimized molecular sieve has uniform pore paths and regular arrangement, and particularly, the pore diameters of the three molecular sieves are matched with those of the liquid phase material heavy naphtha, so that the adsorption and removal of hydrogen sulfide are facilitated.

The heavy naphtha desulfurizer is characterized in that the metal elements of the composite metal oxide include two or three of copper, zinc, magnesium, calcium, nickel, iron and manganese. The corresponding desulfurization reaction temperatures of the oxides of the optimized metal elements are different, namely the corresponding desulfurization reaction temperatures are good at high temperature and the corresponding desulfurization reaction temperatures are good at low temperature, the invention adopts the composition of the oxides of 2 or 3 metal elements, takes account of the desulfurization reaction at high and low temperatures, and is favorable for the dispersion of the composite metal oxides, so that the heavy naphtha desulfurizer prepared by the composition has stronger adaptability to raw materials and process conditions.

In addition, the invention also discloses a method for preparing the heavy naphtha desulfurizer, which comprises the following steps:

dissolving nitrates of two or three metal elements of copper, zinc, magnesium, calcium, nickel, iron and manganese in deionized water, and then heating to 40-70 ℃ to obtain a solution A;

dissolving ammonium salt in deionized water, and heating to 30-50 ℃ to obtain a solution B;

step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 7-10, then heating to 70-90 ℃, standing for 30-120 min, and carrying out suction filtration and washing on the obtained precipitate to obtain a filter cake;

step four, drying the filter cake obtained in the step three, and then roasting to obtain a composite metal oxide;

and step five, adding the composite metal oxide obtained in the step four, active alumina powder, molecular sieve raw powder, dry powder of an organic binder and water into a mixer, uniformly mixing and kneading to obtain a strip material to be extruded, then placing the strip material to be extruded into a forming machine for strip extrusion forming to obtain a strip material, and then drying and roasting the strip material in sequence to obtain the heavy naphtha desulfurizer.

The invention adopts a chemical precipitation method, takes ammonium salt as a precipitator, performs acid-base neutralization reaction with nitrate of metal elements, simultaneously performs molecular rearrangement and secondary crystallization, has uniform crystal grain size, and obtains a precipitate with a composite metal oxide precursor as a main component, because NH in the ammonium salt₄ ⁺And NO₃ ^-Is easily dissolved in water, and then the precipitate can be washed by only a small amount of water to remove most of precipitator components adsorbed in the precipitate, namely NH₄ ⁺And NO₃ ^-To obtain a filter cake, a small part of NH remaining in the filter cake₄ ⁺And NO₃ ^-The catalyst is easy to decompose and remove in the subsequent roasting process, thereby avoiding introducing impurity ions into the heavy naphtha desulfurizer, reducing the washing times, saving the water consumption and facilitating the industrial production; meanwhile, the composite metal oxide obtained by roasting the filter cake, active alumina powder and molecular sieve raw powder are mixed, molded, dried and roasted, and are highly dispersed into the heavy naphtha desulfurizer to form uniformly distributed active sites, and the active alumina with large specific surface area and the molecules with rich pore channelsThe sieve has strong adsorption and diffusion capacity to hydrogen sulfide and mercaptan, effectively promotes the reaction and removal capacity of the composite metal oxide to the sulfide, and greatly improves the purification degree and the sulfur capacity of the heavy naphtha desulfurizer.

The method is characterized in that the total molar concentration of the metal ions in the solution A in the step one is 0.1mol/L^-1～1.0mol/L^-1. By controlling the total molar concentration of the metal ions in the solution A, the reaction rate in the subsequent heating and standing process is favorably and effectively controlled, so that a precipitate with better crystallinity is obtained.

The method is characterized in that the ammonium salt in the step two is ammonium carbonate or ammonium bicarbonate, and the mass concentration of the solution B is 10-15%. The mass concentration of the solution B is controlled to effectively control the reaction rate in the subsequent heating and standing process, so that the precipitate with better crystallinity is obtained.

The method is characterized in that the drying temperature in the fourth step and the drying temperature in the fifth step are both 80-120 ℃ and the drying time is 8-12 hours, the roasting temperature is 300-500 ℃ and the roasting time is 4-6 hours. The drying and roasting process parameters are respectively favorable for fully volatilizing water in the filter cake and fully decomposing organic matters in the composite metal oxide, so that a uniform mesoporous structure is formed.

The method is characterized in that in the fifth step, the organic binder is carboxymethyl cellulose, sesbania powder or tonka-bean powder, and the mass of the organic binder is 3% of the total mass of the composite metal oxide, the activated alumina powder, the molecular sieve raw powder and the dry powder of the organic binder. The preferred type of the binder has moderate molecular weight and good cohesiveness, and simultaneously can form a mesoporous pore channel after being decomposed into gas at high temperature and escaping, thereby improving the pore structure of the desulfurizer.

The method is characterized in that in the fifth step, the mixer is a kneader or a material grinding machine, and the time for uniformly mixing is 20-30 min; the forming machine is a screw rod extruding machine or an oil pressure extruding machine. The optimized time for uniform mixing fully ensures that all materials are uniformly mixed, saves the production time and improves the production efficiency.

Compared with the prior art, the invention has the following advantages:

1. according to the invention, the uniform mixing degree of each metal oxide in the active components is improved by adopting the composite metal oxide, and the active alumina and the molecular sieve are combined to be used as carriers, so that the composite metal oxide is fully dispersed in the active alumina and the molecular sieve, the dispersion degree of the active components is improved, more reaction active sites are provided, and the purification degree and the sulfur capacity of the heavy naphtha desulfurizer are improved.

2. The invention adopts a chemical precipitation method and takes ammonium salt as a precipitator, and NH in the ammonium salt is utilized₄ ⁺And NO in metal nitrates₃ ^-The catalyst is easy to dissolve in water, and a small amount of water is used for washing and subsequent roasting to remove the residual precipitant while the neutralization reaction is realized, so that impurity ions are prevented from being introduced into the desulfurizer, and the industrial production is facilitated.

3. The composite metal oxide, the active alumina powder and the molecular sieve raw powder are mixed, molded, dried and roasted to be highly dispersed in the desulfurizer to form uniformly distributed active sites, and the active alumina with large specific surface area and the molecular sieve with rich pore channels have strong adsorption and diffusion capacities on hydrogen sulfide and mercaptan, so that the reaction removal capacity of the composite metal oxide on sulfide is further promoted, and the purification degree and the sulfur capacity of the heavy naphtha desulfurizer are greatly improved.

4. The heavy naphtha desulfurizer prepared by the invention has the advantages of large specific surface, high sulfur capacity, strong adaptability to raw materials, stable performance and easy industrial production.

The technical solution of the present invention is further described in detail by examples below.

Detailed Description

Example 1

The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: gamma-Al₂O₃50 percent, 10 percent of ZSM-5 molecular sieve and 40 percent of composite metal oxide; the metal elements in the composite metal oxide are copper and nickel.

The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:

step one, dissolving 1000g of copper nitrate and 500g of nickel nitrate in deionized water, and then heating to 40 ℃ to obtain a solution A; the total molar concentration of the metal ions in the solution A is 0.1mol/L^-1；

Step two, dissolving 650g of ammonium carbonate in deionized water, and then heating to 50 ℃ to obtain a solution B with the mass concentration of 10%;

step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 7, then heating to 70 ℃, standing for 30min, carrying out suction filtration on the obtained precipitate, and washing for 3 times by using deionized water to obtain a filter cake;

step four, drying the filter cake obtained in the step three at 80 ℃ for 12h, and then roasting at 300 ℃ for 6h to obtain a composite metal oxide;

step five, mixing 640g of the composite metal oxide obtained in the step four with 800g of gamma-Al₂O₃Adding 150g of ZMS-5 molecular sieve raw powder, 48g of carboxymethyl cellulose and 650mL of water into a kneader, uniformly mixing and kneading for 20min to obtain a strip material to be extruded, then placing the strip material to be extruded into a double-screw strip extruder for extrusion molding to obtain a strip material with phi 3mm multiplied by 5mm (diameter multiplied by length), drying the strip material at 120 ℃ for 8h, and roasting at 500 ℃ for 4h to obtain the heavy naphtha desulfurizer which is recorded as DS-1.

Example 2

The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: AlOOH nH₂10% of O, 50% of 13X molecular sieve and 40% of composite metal oxide; the metal elements in the composite metal oxide are copper, zinc and nickel.

The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:

step one, dissolving 500g of copper nitrate, 600g of zinc nitrate and 200g of nickel nitrate in deionized water, and then heating to 70 ℃ to obtain a solution A; the total molar concentration of the metal ions in the solution A is 0.5mol/L^-1；

Step two, dissolving 600g of ammonium carbonate in 4200mL of deionized water, and then heating to 30 ℃ to obtain a solution B with the mass concentration of 12.5%;

step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 8.5, then heating to 90 ℃, standing for 75min, carrying out suction filtration on the obtained precipitate, and washing for 3 times by using deionized water to obtain a filter cake;

step four, drying the filter cake obtained in the step three at 100 ℃ for 10 hours, and then roasting at 400 ℃ for 5 hours to obtain a composite metal oxide;

step five, mixing 550g of the composite metal oxide obtained in the step four with 230g of AlOOH & nH₂Adding O, 700g of 13X molecular sieve raw powder, 45g of sesbania powder and 600mL of water into a kneader, uniformly mixing and kneading for 25min to obtain a strip material to be extruded, then placing the strip material to be extruded into a double-screw strip extruder for extrusion molding to obtain a strip material with the diameter of phi 3mm multiplied by 5mm (the diameter multiplied by the length), drying the strip material at 80 ℃ for 12h, and roasting at 300 ℃ for 6h to obtain the heavy naphtha desulfurizer which is marked as DS-2.

Example 3

The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: gamma-Al₂O₃35 percent, 35 percent of Y-type molecular sieve and 30 percent of composite metal oxide; the metal elements in the composite metal oxide are manganese, iron and nickel.

The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:

step one, dissolving 450g of manganese nitrate, 450g of ferric nitrate and 420g of nickel nitrate in deionized water, and then heating to 55 ℃ to obtain a solution A; the total molar concentration of the metal ions in the solution A is 1.0mol/L^-1；

Step two, dissolving 600g of ammonium carbonate in 3400mL of deionized water, and then heating to 40 ℃ to obtain a solution B with the mass concentration of 15%;

step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 8.5, then heating to 80 ℃, standing for 120min, carrying out suction filtration on the obtained precipitate, and washing for 3 times by using deionized water to obtain a filter cake;

step four, drying the filter cake obtained in the step three at 120 ℃ for 8 hours, and then roasting at 500 ℃ for 4 hours to obtain a composite metal oxide;

step five, 688g of the composite metal oxide obtained in the step four and 800g of gamma-Al₂O₃Adding 700g of Y-type molecular sieve raw powder, 70g of tonka bean powder and 950mL of water into a grinding machine, uniformly mixing and kneading for 30min to obtain a material to be extruded, then placing the material to be extruded into a double-screw extruder for extrusion molding to obtain a strip material with phi of 3mm multiplied by 5mm (diameter multiplied by length), drying the strip material at 80 ℃ for 12h, and roasting at 300 ℃ for 6h to obtain a heavy naphtha desulfurizer which is recorded as DS-3.

Example 4

The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: AlOOH nH₂20% of O, 10% of 13X molecular sieve, 10% of Y-type molecular sieve and 60% of composite metal oxide; the metal elements in the composite metal oxide are copper, iron and manganese.

The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:

step one, 600g of copper nitrate, 600g of ferric nitrate and 500g of manganese nitrate are dissolved in deionized water, and then heated to 70 ℃ to obtain a solution A; the total molar concentration of the metal ions in the solution A is 1.0mol/L^-1；

Dissolving 900g of ammonium carbonate in 5100mL of deionized water, and heating to 50 ℃ to obtain a solution B with the mass concentration of 15%;

step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 10, then heating to 90 ℃, standing for 120min, carrying out suction filtration on the obtained precipitate, and washing for 3 times by using deionized water to obtain a filter cake;

step four, drying the filter cake obtained in the step three at 110 ℃ for 10h, and then roasting at 450 ℃ for 5h to obtain a composite metal oxide;

step five, 895g of the composite metal oxide obtained in the step four and 400g of AlOOH & nH₂Adding O, 150g of 13X molecular sieve raw powder, 150g of Y-type molecular sieve powder, 45g of carboxymethyl cellulose and 600mL of water into a material grinding machine, uniformly mixing and kneading for 20min to obtain a strip material to be extruded, then placing the strip material to be extruded into a double-screw strip extruding machine for strip extrusion molding to obtain a strip material with phi of 3mm multiplied by 5mm (diameter multiplied by length), drying the strip material at 110 ℃ for 10h, and roasting at 350 ℃ for 6h to obtain a heavy naphtha desulfurizer which is recorded as DS-4.

Example 5

The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: gamma-Al₂O₃27.5 percent of Y-type molecular sieve, 17.5 percent of ZMS-5 molecular sieve and 45 percent of composite metal oxide; the metal elements in the composite metal oxide are copper, calcium and zinc.

The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:

step one, dissolving 500g of copper nitrate, 600g of calcium nitrate and 400g of zinc nitrate in deionized water, and then heating to 60 ℃ to obtain a solution A; the total molar concentration of the metal ions in the solution A is 1.0mol/L^-1；

Step two, dissolving 700g of ammonium carbonate in 6300mL of deionized water, and then heating to 40 ℃ to obtain a solution B with the mass concentration of 10%;

step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 10, then heating to 80 ℃, standing for 90min, carrying out suction filtration on the obtained precipitate, and washing for 3 times by using deionized water to obtain a filter cake;

step four, drying the filter cake obtained in the step three at 90 ℃ for 10h, and then roasting at 450 ℃ for 6h to obtain a composite metal oxide;

step five, 590g of the composite metal oxide obtained in the step four and 350g of gamma-Al₂O₃225g of Y-type molecular sieve raw powder, 125g of ZMS-5 molecular sieve, 40g of carboxymethyl cellulose and 650mL of water are added into a material grinding machine to be uniformly mixed and kneaded for 15min to obtain the material to be extrudedAnd (3) strip materials are placed in a double-screw rod extruder to be extruded and molded to obtain strip materials with the diameter of phi 3mm multiplied by 5mm (the diameter is multiplied by the length), the strip materials are dried at the temperature of 120 ℃ for 8 hours and are roasted at the temperature of 400 ℃ for 5 hours to obtain the heavy naphtha desulfurizer which is recorded as DS-5.

Example 6

The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: gamma-Al₂O₃43 percent of ZSM-5 molecular sieve, 9 percent of Y-type molecular sieve, 9 percent of 13X molecular sieve and 30 percent of composite metal oxide; the metal elements in the composite metal oxide are zinc and iron.

The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:

step one, dissolving 500g of zinc nitrate and 400g of ferric nitrate in deionized water, and then heating to 70 ℃ to obtain a solution A; the total molar concentration of the metal ions in the solution A is 1.0mol/L^-1；

Step two, dissolving 330g of ammonium bicarbonate in 1900mL of deionized water, and then heating to 50 ℃ to obtain a solution B with the mass concentration of 15%;

step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 7, then heating to 85 ℃, standing for 100min, carrying out suction filtration on the obtained precipitate, and washing for 3 times by using deionized water to obtain a filter cake;

step four, drying the filter cake obtained in the step three at 110 ℃ for 12h, and then roasting at 450 ℃ for 6h to obtain a composite metal oxide;

step five, mixing 340g of the composite metal oxide obtained in the step four with 500g of gamma-Al₂O₃100g of ZMS-5 molecular sieve raw powder, 100g of Y-type molecular sieve raw powder, 100g of 13X molecular sieve raw powder, 35g of sesbania powder and 450mL of water are added into a grinding machine to be uniformly mixed and kneaded for 20min to obtain a strip material to be extruded, then the strip material to be extruded is placed into an oil pressure strip extruding machine to be extruded and molded to obtain a strip material with phi of 3mm multiplied by 5mm (diameter multiplied by length), the strip material is dried at 110 ℃ for 12h and roasted at 450 ℃ for 6h to obtain a heavy naphtha desulfurizer which is recorded as DS-6.

Example 7

The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: gamma-Al₂O₃23 percent, 13X molecular sieve 37 percent and composite metal oxide 40 percent; the metal elements in the composite metal oxide are magnesium and copper.

The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:

step one, dissolving 700g of magnesium nitrate and 800g of copper nitrate in deionized water, and then heating to 70 ℃ to obtain a solution A; the total molar concentration of the metal ions in the solution A is 1.0mol/L^-1；

Step two, dissolving 650g of ammonium carbonate in 3680mL of deionized water, and then heating to 50 ℃ to obtain a solution B with the mass concentration of 15%;

step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 7.5, then heating to 85 ℃, standing for 90min, carrying out suction filtration on the obtained precipitate, and washing for 4 times by using deionized water to obtain a filter cake;

step four, drying the filter cake obtained in the step three at 100 ℃ for 12 hours, and then roasting at 450 ℃ for 6 hours to obtain a composite metal oxide;

step five, mixing 530g of the composite metal oxide obtained in the step four with 300g of gamma-Al₂O₃Adding 500g of 13X molecular sieve raw powder, 27g of tonka bean powder and 550mL of water into a grinding machine, uniformly mixing and kneading for 20min to obtain a material to be extruded, then placing the material to be extruded into a double-screw extruder for extrusion molding to obtain a strip material with phi of 3mm multiplied by 5mm (diameter multiplied by length), drying the strip material at 80 ℃ for 12h, and roasting at 350 ℃ for 6h to obtain a heavy naphtha desulfurizer which is recorded as DS-7.

Example 8

The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: AlOOH nH₂O36%, 13X molecular sieve 14% and composite metal oxide 50%; the metal elements in the composite metal oxide are calcium and nickel.

The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:

step one, dissolving 1000g of calcium nitrate and 500g of nickel nitrate in deionized water, and then heating to 60 ℃ to obtain a solution A; the total molar concentration of the metal ions in the solution A is 1.0mol/L^-1；

Step two, dissolving 700g of ammonium carbonate in 4900mL of deionized water, and then heating to 50 ℃ to obtain a solution B with the mass concentration of 12.5%;

step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 10, then heating to 80 ℃, standing for 60min, carrying out suction filtration on the obtained precipitate, and washing for 3 times by using deionized water to obtain a filter cake;

step four, drying the filter cake obtained in the step three at 120 ℃ for 8 hours, and then roasting at 500 ℃ for 4 hours to obtain a composite metal oxide;

step five, 546g of the composite metal oxide obtained in the step four and 540g of AlOOH & nH₂Adding O, 150g of 3X molecular sieve raw powder, 30g of carboxymethyl cellulose and 500mL of water into a kneader, uniformly mixing and kneading for 30min to obtain a strip material to be extruded, then placing the strip material to be extruded into a double-screw strip extruder for extrusion molding to obtain a strip material with the diameter of phi 3mm multiplied by 5mm (the diameter multiplied by the length), drying the strip material at 120 ℃ for 8h, and roasting at 450 ℃ for 6h to obtain the heavy naphtha desulfurizer which is recorded as DS-8.

Example 9

The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: gamma-Al₂O₃30 percent, 10 percent of Y-type molecular sieve and 60 percent of composite metal oxide; the metal elements in the composite metal oxide are copper and zinc.

The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:

step one, dissolving 1000g of copper nitrate and 950g of zinc nitrate in deionized water, and then heating to 70 ℃ to obtain a solution A; the total molar concentration of the metal ions in the solution A is 1.0mol/L^-1；

Step two, dissolving 850g of ammonium carbonate in 7650mL of deionized water, and then heating to 40 ℃ to obtain a solution B with the mass concentration of 10%;

step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 8, then heating to 85 ℃, standing for 120min, carrying out suction filtration on the obtained precipitate, and washing for 3 times by using deionized water to obtain a filter cake;

step four, drying the filter cake obtained in the step three at 110 ℃ for 10h, and then roasting at 350 ℃ for 6h to obtain a composite metal oxide;

step five, mixing 830g of the composite metal oxide obtained in the step four with 410g of gamma-Al₂O₃Adding 135g of Y-type molecular sieve raw powder, 30g of carboxymethyl cellulose and 600mL of water into a grinding machine, uniformly mixing and kneading for 20min to obtain a strip material to be extruded, then placing the strip material to be extruded into a double-screw strip extruder for strip extrusion molding to obtain a strip material with the diameter of phi 3mm multiplied by 5mm (the diameter multiplied by the length), drying the strip material at 110 ℃ for 12h, and roasting at 450 ℃ for 4h to obtain a heavy naphtha desulfurizer which is recorded as DS-9.

Comparative example 1

The heavy naphtha desulfurizer of the comparative example consists of the following components in percentage by mass: gamma-Al₂O₃30 percent of bentonite, 10 percent of bentonite and 60 percent of composite metal oxide; the metal elements in the composite metal oxide are copper and zinc.

The preparation method of the heavy naphtha desulfurizer of the comparative example comprises the following steps:

step one, dissolving 1000g of copper nitrate and 950g of zinc nitrate in deionized water, and then heating to 70 ℃ to obtain a solution A; the total molar concentration of the metal ions in the solution A is 1.0mol/L^-1；

Step two, dissolving 850g of ammonium carbonate in 7650mL of deionized water, and then heating to 40 ℃ to obtain a solution B with the mass concentration of 10%;

step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 8, then heating to 85 ℃, standing for 120min, carrying out suction filtration on the obtained precipitate, and washing for 3 times by using deionized water to obtain a filter cake;

step four, drying the filter cake obtained in the step three at 110 ℃ for 10h, and then roasting at 350 ℃ for 6h to obtain a composite metal oxide;

step five, mixing 830g of the composite metal oxide obtained in the step four with 410g of gamma-Al₂O₃144g of bentonite, 30g of carboxymethyl cellulose and 600mL of water are added into a material grinding machine to be uniformly mixed and kneaded for 20min to obtain a material to be extruded, then the material to be extruded is placed into a double-screw extruder to be extruded and molded to obtain a material with phi of 3mm multiplied by 5mm (diameter multiplied by length), the material is dried at 110 ℃ for 12h and roasted at 450 ℃ for 4h to obtain a heavy naphtha desulfurizer which is marked as CDS-1.

Comparative example 2

The heavy naphtha desulfurizer of the comparative example consists of the following components in percentage by mass: gamma-Al₂O₃30 percent of Y-type molecular sieve, 10 percent of copper oxide and 30 percent of zinc oxide.

The preparation method of the heavy naphtha desulfurizer of the comparative example comprises the following steps: 415g of copper oxide powder, 415g of zinc oxide powder and 410g of gamma-Al₂O₃Adding 135g of Y-type molecular sieve raw powder, 30g of carboxymethyl cellulose and 600mL of water into a grinding machine, uniformly mixing and kneading for 20min to obtain a strip material to be extruded, then placing the strip material to be extruded into a double-screw strip extruder for strip extrusion molding to obtain a strip material with the diameter of phi 3mm multiplied by 5mm (the diameter multiplied by the length), drying the strip material at 110 ℃ for 12h, and roasting at 450 ℃ for 4h to obtain a heavy naphtha desulfurizer which is recorded as CDS-2.

Comparative example 3

The heavy naphtha desulfurizer of the comparative example consists of the following components in percentage by mass: gamma-Al₂O₃30 percent, 10 percent of Y-type molecular sieve and 60 percent of composite metal oxide; the metal elements in the composite metal oxide are copper and zinc.

The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:

step one, dissolving 1000g of copper nitrate and 950g of zinc nitrate in deionized water, and then heating to 70 ℃ to obtain a solution A; the solution AThe total molar concentration of the metal ions in the solution is 1.0mol/L^-1；

Step two, dissolving 850g of sodium carbonate in 7650mL of deionized water, and then heating to 40 ℃ to obtain a solution B with the mass concentration of 10%;

step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 8, then heating to 85 ℃, standing for 120min, carrying out suction filtration on the obtained precipitate, and washing for 3 times by using deionized water to obtain a filter cake;

step four, drying the filter cake obtained in the step three at 110 ℃ for 10h, and then roasting at 350 ℃ for 6h to obtain a composite metal oxide;

step five, mixing 830g of the composite metal oxide obtained in the step four with 410g of gamma-Al₂O₃Adding 135g of Y-type molecular sieve raw powder, 30g of carboxymethyl cellulose and 600mL of water into a grinding machine, uniformly mixing and kneading for 20min to obtain a strip material to be extruded, then placing the strip material to be extruded into a double-screw strip extruder for strip extrusion molding to obtain a strip material with the diameter of phi 3mm multiplied by 5mm (the diameter multiplied by the length), drying the strip material at 110 ℃ for 12h, and roasting at 450 ℃ for 4h to obtain a heavy naphtha desulfurizer which is recorded as CDS-3.

Example 10

The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: gamma-Al₂O₃35 percent, 13X type molecular sieve 20 percent and composite metal oxide 45 percent; the metal elements in the composite metal oxide are copper and iron.

The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:

step one, dissolving 400g of copper nitrate and 600g of ferric nitrate in deionized water, and then heating to 70 ℃ to obtain a solution A; the total molar concentration of the metal ions in the solution A is 1.0mol/L^-1；

Step two, dissolving 450g of ammonium carbonate in 2550mL of deionized water, and then heating to 30 ℃ to obtain a solution B with the mass concentration of 15%;

step three, dropwise adding the solution A obtained in the step one into the solution B obtained in the step two under the condition of continuous stirring for reaction, controlling the pH of a reaction system to be 7, then heating to 80 ℃, standing for 60min, carrying out suction filtration on the obtained precipitate, and washing for 4 times by using deionized water to obtain a filter cake;

step four, drying the filter cake obtained in the step three at 120 ℃ for 8 hours, and then roasting at 350 ℃ for 6 hours to obtain a composite metal oxide;

step five, 560g of the composite metal oxide obtained in the step four and 450g of gamma-Al₂O₃Adding 250g of 13X type molecular sieve raw powder, 25g of carboxymethyl cellulose and 500mL of water into a material grinding machine, uniformly mixing and kneading for 20min to obtain a strip material to be extruded, then placing the strip material to be extruded into a double-screw strip extruding machine for strip extrusion molding to obtain a strip material with phi 3mm multiplied by 5mm (diameter multiplied by length), drying the strip material at 100 ℃ for 10h, and roasting at 400 ℃ for 4h to obtain a heavy naphtha desulfurizer which is recorded as DS-10.

Respectively crushing the heavy naphtha desulfurizer in the embodiments 1 to 10 and the comparative examples 1 to 3 to 20 meshes, respectively weighing 3mL of the heavy naphtha desulfurizer, filling the heavy naphtha into a middle constant-temperature zone of a stainless steel reactor with the diameter of 10mm multiplied by 600mm (diameter multiplied by length), filling two ends of the stainless steel reactor with 20 to 40 meshes of quartz sand, desulfurizing the heavy naphtha at the reaction temperature of 150 ℃, the pressure of normal pressure and the feeding amount of the heavy naphtha of 20mL/h, and inspecting the purification degree and the sulfur capacity of the heavy naphtha desulfurizer, wherein the content of hydrogen sulfide in the raw material heavy naphtha is 4.75 mu g^-1The mercaptan content was 2. mu.g.g^-1(ii) a When the total sulfur content at the outlet of the stainless steel reactor exceeds 0.5 mu g^-1When the oil is considered to have penetrated, the desulfurization treatment is stopped, the desulfurizing agent is taken out and the sulfur capacity of each heavy naphtha desulfurizing agent is analyzed, and the results are shown in the following table 1.

The sulfur capacity calculation formula is as follows:

in the formula: s- -sulfur capacity, which represents the capacity of the desulfurizing agent to remove hydrogen sulfide, unit%

C₁- - -stainless steelSulfur content in units of ug g in heavy naphtha at reactor inlet^-1；

C₂Sulfur content in units of mug at the outlet of a stainless steel reactor^-1；

Q- - -total mass of heavy naphtha passing through the desulfurizer at breakthrough, in g;

m is the weight of the heavy naphtha desulfurizer, unit g.

TABLE 1

Note: the total sulfur content in table 1 was measured by coulometry, and the sulfur capacity was measured by combustion.

As can be seen from table 1, the heavy naphtha desulfurizer in examples 1 to 10 of the present invention has a good reaction removal capability for sulfides, and greatly improves the purification degree and sulfur capacity of the heavy naphtha desulfurizer; the sulfur capacity and the purification degree of the heavy naphtha desulfurizer DS-9 in example 9 are higher than those of CDS-1 to CDS-3 in comparative examples 1 to 3, which shows that the invention adopts the composite metal oxide to improve the uniform mixing degree of each metal oxide in the active component, and combines the active alumina and the molecular sieve as the carrier, so that the composite metal oxide is fully dispersed in the active alumina and the molecular sieve, the dispersion degree of the active component is improved, more reaction active sites are provided, and the purification degree and the sulfur capacity of the heavy naphtha desulfurizer are improved.

The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention still belong to the protection scope of the technical solution of the invention.