阅读说明：本技术 一种常温液态烃脱硫剂及其制备方法 (Normal-temperature liquid hydrocarbon desulfurizer and preparation method thereof ) 是由 任家君 邓国伟 毛满意 罗念 常贺飞 霍晓剑 白雪琴 常思乔 武卫华 熊丽霞 黄 于 2019-12-04 设计创作，主要内容包括：本发明公开一种常温液态烃脱硫剂及其制备方法,该常温液态烃脱硫剂,以质量百分比计,由以下原料组成：铜锌复合氧化物50％～85％,助催化剂1％～18％,铝胶载体5％～20％,粘合剂1％～15％。本发明提供的常温液态烃脱硫剂通过利用氧化态金属脱除硫化氢,利用还原态金属脱除元素硫和硫醇,从而将油品中多种形态的硫化物脱除到较低水平,保证油品铜片腐蚀合格、银片腐蚀合格。(The invention discloses a normal-temperature liquid hydrocarbon desulfurizer and a preparation method thereof, wherein the normal-temperature liquid hydrocarbon desulfurizer consists of the following raw materials in percentage by mass: 50-85% of copper-zinc composite oxide, 1-18% of cocatalyst, 5-20% of aluminum glue carrier and 1-15% of adhesive. The normal-temperature liquid hydrocarbon desulfurizer provided by the invention removes hydrogen sulfide by using oxidation state metal and removes element sulfur and mercaptan by using reduction state metal, thereby removing sulfides in various forms in oil products to a lower level, and ensuring that copper sheet corrosion of the oil products is qualified and silver sheet corrosion of the oil products is qualified.)

1. The normal-temperature liquid hydrocarbon desulfurizer is characterized by comprising the following raw materials by mass percent:

50-85% of copper-zinc composite oxide, 1-18% of cocatalyst, 5-20% of aluminum glue carrier and 1-15% of adhesive.

2. The normal-temperature liquid hydrocarbon desulfurizer according to claim 1, wherein the molar ratio of copper oxide to zinc oxide in the copper-zinc composite oxide is 1 (0.5 to 3).

3. The normal-temperature liquid hydrocarbon desulfurizer according to claim 1, wherein the cocatalyst is one or a mixture of several of metal powders of nano-scale copper and nickel.

4. The normal-temperature liquid hydrocarbon desulfurizer according to claim 1, wherein the binder is one or a mixture of several of carboxymethyl cellulose, starch, calcium oxide, bentonite and kaolin.

5. A preparation method of the normal-temperature liquid hydrocarbon desulfurizer as claimed in any one of claims 1 to 4, comprising the following steps:

preparing a copper-zinc composite oxide; preparing an alumina gel carrier; preparing mixed precipitate; mixing and forming; and (5) roasting and activating.

6. The preparation method of the normal-temperature liquid hydrocarbon desulfurizer as claimed in claim 5, wherein the specific steps of preparing the copper-zinc composite oxide comprise: dissolving soluble copper salt and soluble zinc salt in water to prepare a copper-zinc mixed solution, and then taking weak base as a precipitator to obtain copper-zinc composite oxide precipitate by adopting a coprecipitation method; wherein the molar ratio of the weak base to the metal cations in the copper-zinc mixed salt solution is (1.5-3) to 1.

7. The preparation method of the normal-temperature liquid hydrocarbon desulfurizer as claimed in claim 5, wherein the specific steps of preparing the aluminum cement carrier comprise: will contain Al³⁺Dissolving the soluble salt in water to prepare an aluminum salt solution, and then precipitating Al by using weak base³⁺Obtaining an alumina gel carrier; wherein the weak base is mixed with Al³⁺The molar ratio of (2.0-3.5): 1.

8. a preparation method of a normal temperature liquid hydrocarbon desulfurizer as claimed in claim 6 or 7, characterized in that the weak base is one or a mixture of more of alcohol amine, urea, sodium carbonate, sodium bicarbonate and ammonium bicarbonate.

9. The method for preparing a normal-temperature liquid hydrocarbon desulfurizing agent according to claim 5, wherein the concrete steps of preparing the mixed precipitate include: and mixing the aluminum colloid carrier and the copper-zinc composite oxide precipitate, and continuously reacting to obtain a mixed precipitate.

10. The preparation method of the normal-temperature liquid hydrocarbon desulfurizer as claimed in claim 5, wherein the specific steps of mixing and molding comprise: centrifugally washing, drying and grinding the mixed precipitate into powder, adding a certain amount of binder and cocatalyst, uniformly mixing, and kneading for molding;

the roasting activation comprises the following specific steps: and naturally airing the formed desulfurizer at room temperature, curing, putting into a drying room, and drying and activating to obtain the normal-temperature liquid hydrocarbon desulfurizer.

Technical Field

The invention relates to the technical field of environmental protection and petrochemical industry, in particular to a normal-temperature liquid hydrocarbon desulfurizer and a preparation method thereof.

Background

With the rapid development of civil aviation industry and national defense industry in China, the demand of aviation kerosene is continuously increased, and the quality requirement of aviation kerosene is gradually improved. The raw materials for producing the aviation kerosene mainly comprise straight-run aviation kerosene fractions and hydrofining fractions. These fractions inevitably carry over a certain amount of active sulfur compounds, such as elemental sulfur (S)⁰) Hydrogen sulfide (H)₂S), mercaptan (RSH) and the like, wherein the sulfides are the main reasons for the unqualified metal inspection of oil products such as aviation kerosene, naphtha and the like. In order to ensure the safety of flight and prevent sulfide in the aviation kerosene from corroding key parts such as an engine and the like, the sulfur content in the aviation kerosene product must be strictly controlled.

The sulfur content is already at a low level by the jet fuel after the upstream refining, but metal corrosion problems still occur. The unqualified aviation kerosene metal corrosion is mainly caused by different aviation kerosene production processes, different forms of sulfides brought from upstream and elemental sulfur (S)⁰) Hydrogen sulfide (H)₂S), mercaptan (RSH) and other active sulfur can generate superimposed corrosion and circulating corrosion, and the problem of unqualified corrosion cannot be fundamentally solved by singly removing a certain sulfide. Therefore, the key point for solving the problem of aviation kerosene metal corrosion is to prepare the multifunctional desulfurizing agent and remove active sulfides in various forms.

Chinese patent document CN1361230A discloses a preparation method of an aviation kerosene liquid-phase normal-temperature fine desulfurizing agent, wherein ZnO is adopted as a main active component, and TiO is adopted as a desulfurizing agent₂NiO, etc. as co-catalyst, with Al₂O₃Is prepared by carrier, but the desulfurizer is mainly used for removing hydrogen sulfide in aviation keroseneThe problem of unqualified silver sheet corrosion caused by hydrogen sulfide is solved, and the problem of corrosion caused by elemental sulfur and mercaptan cannot be solved.

Chinese patent document CN1284538A discloses a method for normal temperature dry-process fine desulfurization of liquid hydrocarbon, which adopts a combined bed of composite oxide and activated carbon to remove hydrogen sulfide and elemental sulfur in liquid hydrocarbon in two steps. The process is mainly used for removing sulfides in light oil products such as liquefied gas, propane, butane and the like, so that the corrosion of copper sheets is less than or equal to level 1, and the process does not mention whether the process is suitable for removing sulfides in aviation kerosene or not, and has unknown application effect on the problem of silver sheet corrosion. Meanwhile, the composite desulfurizer involved in the desulfurization process mainly adopts composite oxides of iron and zinc as active components, can only be used for removing hydrogen sulfide, and the removal of elemental sulfur and mercaptan is completed by means of another active carbon desulfurizer in the process, so that the process is complex.

Chinese patent document CN106268619A discloses a preparation method of a normal temperature oil product desulfurizer, which is prepared by using zinc oxide as a main active component, metals such as copper, silver, iron and the like and oxides thereof as a cocatalyst, pseudo-boehmite and the like as a carrier and a binder. The silver used in the method is noble metal, so the method has high economic cost and limited addition amount. Secondly, citric acid used in the preparation process of the desulfurizer can not be completely separated from the product, so that the desulfurizer is easy to absorb moisture in the use process to reduce the strength.

In conclusion, the development of a normal temperature liquid hydrocarbon desulfurizing agent capable of simultaneously removing a plurality of active sulfides remains one of the technical problems to be solved in the field.

Disclosure of Invention

The invention aims to overcome the technical defects and provides a normal-temperature liquid hydrocarbon desulfurizer and a preparation method thereof.

In order to achieve the technical purpose, the first solution of the invention provides a normal-temperature liquid hydrocarbon desulfurizer, which comprises the following raw materials in percentage by mass: 50-85% of copper-zinc composite oxide, 1-18% of cocatalyst, 5-20% of aluminum glue carrier and 1-15% of adhesive.

The second solution of the invention provides a preparation method of a normal-temperature liquid hydrocarbon desulfurizer, which comprises the following steps: preparing a copper-zinc composite oxide; preparing an alumina gel carrier; preparing mixed precipitate; mixing and forming; and (5) roasting and activating.

The preparation method of the normal-temperature liquid hydrocarbon desulfurizer provided in the second solution is used for preparing the normal-temperature liquid hydrocarbon desulfurizer provided in the first solution.

Compared with the prior art, the invention has the beneficial effects that:

the normal-temperature liquid hydrocarbon desulfurizer provided by the invention removes hydrogen sulfide by using oxidation state metal and removes element sulfur and mercaptan by using reduction state metal, thereby removing sulfides in various forms in oil products to a lower level, and ensuring that copper sheet corrosion of the oil products is qualified and silver sheet corrosion of the oil products is qualified.

Drawings

FIG. 1 is a process flow diagram of an embodiment of the method for preparing a normal-temperature liquid hydrocarbon desulfurizing agent according to the present invention;

FIG. 2 is a schematic structural view of a desulfurizing agent dynamic evaluation test apparatus.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

For the first solution scheme of the invention, the invention provides a normal-temperature liquid hydrocarbon desulfurizer which comprises the following raw materials in percentage by mass:

50-85% of copper-zinc composite oxide, 1-18% of cocatalyst, 5-20% of aluminum glue carrier and 1-15% of adhesive. Wherein, in the copper-zinc composite oxide, the molar ratio of copper oxide to zinc oxide is 1 (0.5-3), preferably 1 (0.8-2); the cocatalyst is one or a mixture of several of metal powders of nano-copper and nickel; the binder is one or more of carboxymethyl cellulose, starch, calcium oxide, bentonite and kaolin.

In the invention, copper, zinc and oxides thereof are selected as main active components, so that the desulfurizing agent has higher desulfurizing precision compared with metals such as iron, manganese and the like, particularly has strong affinity and higher vulcanizing equilibrium constant for hydrogen sulfide, and can obviously improve the desulfurizing precision of the desulfurizing agent.

In the invention, metal powder of copper and nickel is selected as a cocatalyst, so that elemental sulfur and partial mercaptan in oil products can be effectively removed, and metals such as zinc, iron, manganese and the like do not have the function; meanwhile, the addition of the copper and nickel metal powder can effectively improve the reaction potential energy of the desulfurizer on various sulfides, and the phenomenon of 'reversion' can not occur.

As for the second solution of the present invention, the present invention provides a method for preparing a normal temperature liquid hydrocarbon desulfurizing agent, as shown in fig. 1, comprising the following steps: s1, preparing a copper-zinc composite oxide; s2, preparing an aluminum gel carrier; s3, preparing mixed precipitates; s4, mixing and forming; and S5, roasting and activating.

The preparation method of the normal-temperature liquid hydrocarbon desulfurizer provided in the second solution is used for preparing the normal-temperature liquid hydrocarbon desulfurizer provided in the first solution.

In the invention, the specific steps for preparing the copper-zinc composite oxide comprise: selecting proper soluble copper salt and soluble zinc salt, dissolving in water according to a certain proportion to prepare copper-zinc mixed solution, then using weak base as precipitant, adopting coprecipitation method to obtain copper-zinc composite oxide precipitate S₁. Wherein, in the copper-zinc mixed solution, the concentration of copper salt is 0.1-0.6 mol/L, the concentration of zinc salt is 0.2-0.6 mol/L, and the molar ratio of copper salt to zinc salt is 1 (0.5-3), preferably 1 (0.8-2); the mass concentration of the weak base is 10-25%; in the coprecipitation process, the molar ratio of the weak base to the metal cations in the copper-zinc mixed salt solution is (1.5-3): 1, the alkali-dropping salt is used in a dropping mode, the stirring speed is 300-600 r/min, the reaction temperature is 40-60 ℃, and the reaction is carried out at reverse reactionThe reaction time is 1-3 h.

Specifically, the soluble copper salt is CuSO₄、CuCl₂、Cu(NO₃)₂One or a mixture of several of them; the soluble zinc salt is ZnSO₄、ZnCl₂、Zn(NO₃)₂One or a mixture of several of them; the weak base is one or more of alcohol amine, urea, sodium carbonate, sodium bicarbonate and ammonium bicarbonate.

In the invention, the specific steps for preparing the alumina gel carrier comprise: will contain Al³⁺Dissolving the soluble salt in water to prepare an aluminum salt solution with a certain concentration, and precipitating Al by using weak base under a certain condition³⁺Obtaining the alumina gel carrier. Wherein, in the aluminum salt solution, Al³⁺The concentration of (A) is 0.2-1.5 mol/L; the mass concentration of the weak base is 5-15%; in the process of obtaining the alumina gel carrier, weak base and Al are mixed³⁺The molar ratio of (2.0-3.5): 1, adopting a positive dropping method of dropping salt with alkali in a dropping mode, wherein the stirring speed is 300-600 r/min, the reaction temperature is 60-80 ℃, the reaction time is 1-3 h, and the aging time is 24 h.

Specifically, the aluminum salt is AlCl₃Or Al₂(SO4)₃One or a mixture of several of them; the weak base is one or more of alcohol amine, urea, sodium carbonate, sodium bicarbonate and ammonium bicarbonate.

In the invention, weak bases such as alcohol amine, urea, sodium carbonate, sodium bicarbonate, ammonium bicarbonate and the like are selected as the precipitating agent, and compared with strong bases such as sodium hydroxide, ammonia water and the like, the precipitating agent has the following obvious advantages:

a. weak bases such as alcohol amine, urea, sodium carbonate, sodium bicarbonate and ammonium bicarbonate are not as alkaline as ammonia water and sodium hydroxide, so that the pH value of the system has controllability and wide-range adjustability, the weak bases are slowly ionized in an aqueous solution, precipitation reaction is orderly carried out, and system errors and human errors caused by the dropping speed and the concentration of alkali liquor are effectively avoided.

b. Weak bases such as alcohol amine, urea, sodium carbonate, sodium bicarbonate and ammonium bicarbonate play multiple roles in the reaction, and are used as a precipitator, a dispersing agent and a template agent, so that the metal oxide prepared by the weak bases has a developed pore structure, a higher specific surface, a narrower pore size distribution and a highly dispersed active center, and has more excellent desulfurization activity.

In the invention, the concrete steps for preparing the mixed precipitate comprise: precipitating S by aluminum colloid carrier and the copper-zinc composite oxide₁Mixing, reacting for a while to obtain mixed precipitate S₂. Wherein, in the process of continuing the reaction, the stirring speed is 300-600 r/min, the reaction temperature is 40-60 ℃, and the reaction time is 1-3 h.

In the invention, the coprecipitation method is adopted to prepare the active component, compared with the blending method, the operation is more exquisite, the diameter of the prepared active particle is smaller, the active center is more dispersed, the pore structure is richer, the synergistic effect between the main active component and the cocatalyst is more obvious, the adsorption rate and the reaction rate are accelerated, and the fine removal of trace sulfides is facilitated.

In the invention, the mixing and molding steps comprise: mixing the precipitate S₂Centrifugally washing, drying, grinding into powder, adding a certain amount of binder and cocatalyst, uniformly mixing, kneading and forming. Wherein the drying mode of the mixed precipitate is natural drying or cold air drying, and the drying time is 12-24 hours; the kneading molding mode is one of screw extrusion molding and hydraulic sheet forming.

In the invention, the roasting activation comprises the following specific steps: and (3) naturally airing the formed desulfurizer at room temperature, curing, putting into a drying room, and drying and activating under certain conditions to obtain the normal-temperature liquid hydrocarbon desulfurizer. Wherein, the drying and activating mode is as follows: and drying the mixture at 200-260 ℃ for 2-4 h by using nitrogen.

In the invention, alumina sol (namely an alumina sol carrier) is used as a porous carrier of the desulfurizer, and all the alumina sol is converted into active alumina after being roasted at 200-260 ℃. Compared with the impregnation method, the method has the advantages that the active components can be more uniformly dispersed in the pore channels of the porous carrier, so that the utilization rate of the active components is higher. In addition to this, the present invention is,al is not incorporated in the process³⁺Directly together with other metal salts (such as copper salts and zinc salts, etc.) because: the aluminum colloid carrier and the active composite oxide are independently prepared, which is favorable for ensuring the property of the active component and the integrity of the pore channel of the aluminum colloid carrier, and the Al is precipitated by the aluminum sol and other metal active components with different optimal pH values³⁺Precipitation directly with other metal salts can result in leaching of the colloidal aluminum carrier and the active ingredient by dissolution to varying degrees.