CN110791308A - Normal-temperature liquid hydrocarbon desulfurizer and preparation method thereof - Google Patents
Normal-temperature liquid hydrocarbon desulfurizer and preparation method thereof Download PDFInfo
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- CN110791308A CN110791308A CN201911226399.4A CN201911226399A CN110791308A CN 110791308 A CN110791308 A CN 110791308A CN 201911226399 A CN201911226399 A CN 201911226399A CN 110791308 A CN110791308 A CN 110791308A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/16—Metal oxides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
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.
Description
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.
Example 1:
zn (NO) is prepared according to the proportion that the mass fraction of oxides in the desulfurizer is respectively 40 percent and 35 percent3)2And Cu (NO)3)2In the mixed solution of copper and zinc, the concentration of zinc salt is 0.34mol/L, and the concentration of copper salt is 0.30 mol/L; under the condition of water bath at 40 ℃, dripping 15% of ammonium bicarbonate solution into the copper-zinc mixed salt solution, wherein the molar ratio of the ammonium bicarbonate to metal cations in the copper-zinc mixed salt solution is 1.8:1, the stirring speed is 400r/min, the total dripping time is 1h, and after the dripping is finished, continuing to stir for 1.5h under heat preservation to obtain copper-zinc composite oxide precipitate;
weighing AlCl with calculated amount according to the mass fraction of 15% of oxides in the desulfurizer3Preparing 0.4mol/L salt solution, and then dropwise adding 10% ammonium bicarbonate solution into the salt solution under the conditions that the water bath temperature is 80 ℃ and the stirring speed is 400r/min, wherein the salt-base ratio is 1: 2.2; continuing to stir for 1h under heat preservation after the dropwise addition is finished, then stopping stirring and heating, and aging for 24h to obtain alumina sol; slowly pouring the aluminum sol into the copper-zinc composite oxide precipitate, stirring for 1h at the rotating speed of 400r/min in a water bath at 40 ℃, stopping reaction, filtering, washing with clear water, naturally drying, completely oxidizing, and grinding into powder to obtain desulfurizer raw powder S;
and (2) respectively weighing CaO and bentonite as adhesives according to the mass fraction of 4% and 4% of the desulfurizer, meanwhile, weighing copper powder and nickel powder as cocatalyst according to the mass fraction of 1% and 1% of the desulfurizer, uniformly mixing the promoters and the original powder S of the desulfurizer, adding water, kneading for 30min, extruding and molding by using a single-screw extruder, naturally airing at room temperature, curing, then placing in a drying room, and drying and activating at 260 ℃ in a nitrogen atmosphere to obtain the finished product desulfurizer.
Example 2:
ZnCl is prepared according to the proportion that the mass fraction of the oxide in the desulfurizer is 45 percent and 30 percent respectively2And CuCl2In the mixed solution of copper and zinc, the concentration of zinc salt is 0.525mol/L, and the concentration of copper salt is 0.35 mol/L; under the condition of water bath at 50 ℃, dripping 12 percent of urea solution by mass into the copper-zinc mixed salt solution, wherein the molar ratio of ammonium bicarbonate to metal cations in the copper-zinc mixed salt solution is 2.2:1, the stirring speed is 400r/min, the total dripping time is 1h, and after the dripping is finished, continuing to stir for 1.5h under heat preservation to obtain copper-zinc composite oxide precipitate;
weighing AlCl with calculated amount according to the mass fraction of oxide in the desulfurizer of 18 percent3Preparing 0.5mol/L salt solution, and then dropwise adding 12% urea solution into the salt solution under the conditions that the water bath temperature is 80 ℃ and the stirring speed is 400r/min, wherein the salt-base ratio is 1: 2.5; continuing to stir for 1h under heat preservation after the dropwise addition is finished, then stopping stirring and heating, and aging for 24h to obtain alumina sol; slowly pouring the aluminum sol into the copper-zinc composite oxide precipitate, stirring for 1h at the rotating speed of 400r/min in a water bath at 40 ℃, stopping reaction, filtering, washing with clear water, naturally drying, completely oxidizing, and grinding into powder to obtain desulfurizer raw powder S;
the method comprises the steps of weighing CaO, kaolin and carboxymethyl cellulose as adhesives according to the mass fractions of 2%, 1.5% and 1% of a desulfurizer, weighing copper powder and nickel powder as cocatalyst according to the mass fractions of 2% and 0.5% of the desulfurizer, uniformly mixing the promoters and the original powder S of the desulfurizer, adding water, kneading for 30min, extruding and molding by using a single-screw extruder, naturally airing at room temperature, curing, putting into a drying room, and drying and activating at 250 ℃ in a nitrogen atmosphere to obtain the finished product desulfurizer.
Example 3:
preparing ZnSO according to the mass fraction of oxides in the desulfurizer of 50 percent and 25 percent respectively4And CuSO4In the mixed solution of copper and zinc, the concentration of zinc salt is 0.4mol/L, and the concentration of copper salt is 0.2 mol/L; under the condition of water bath at 40 ℃, dripping 8% sodium bicarbonate solution by mass into the copper-zinc mixed salt solution, wherein the molar ratio of the sodium bicarbonate to metal cations in the copper-zinc mixed salt solution is 2.2:1, the stirring speed is 600r/min, the total dripping time is 1h, and after finishing dripping, continuing stirring for 2.0h under heat preservation to obtain copper-zinc composite oxide precipitate;
weighing AlCl with calculated amount according to the mass fraction of oxide in the desulfurizer of 16%3Preparing 0.3mol/L saline solution N, and then dropwise adding 8% sodium bicarbonate solution into the saline solution N under the conditions that the water bath temperature is 80 ℃ and the stirring speed is 400r/min, wherein the salt-base ratio is 1: 2.5; continuing to stir for 1h under heat preservation after the dropwise addition is finished, then stopping stirring and heating, and aging for 24h to obtain alumina sol; slowly pouring the aluminum sol into the copper-zinc composite oxide precipitate, stirring for 1h at the rotating speed of 600r/min in a water bath at 50 ℃, stopping reaction, filtering, washing with clear water, naturally drying, completely oxidizing, and grinding into powder to obtain desulfurizer raw powder S;
weighing kaolin and starch as adhesives according to the mass fraction of 3% and 4% of oxides in the desulfurizer, weighing copper powder and nickel powder as promoters according to the mass fraction of 0.5% and 1.5%, mixing the promoters with the original powder S of the desulfurizer uniformly, adding water, kneading for 30min, extruding and molding by using a single-screw extruder, naturally airing at room temperature, curing, then placing in a drying room, and drying and activating at 240 ℃ in a nitrogen atmosphere to obtain the finished product desulfurizer.
Example 4:
zn (NO) is prepared according to the proportion that the mass fraction of oxides in the desulfurizer is respectively 35 percent and 40 percent3)2And CuSO4In the mixed solution of copper and zinc, the concentration of zinc salt is 0.35mol/L, and the concentration of copper salt is 0.4 mol/L; dropping a diethanolamine solution with the mass fraction of 20% into a copper-zinc mixed salt solution under the water bath condition of 60 ℃, wherein the molar ratio of the diethanolamine to metal cations in the copper-zinc mixed salt solution is 2.5:1, and the stirring speed is 600r/minThe total dropping time is 1h, and after the dropping is finished, the stirring is continued for 2.0h under heat preservation to obtain copper-zinc composite oxide precipitate;
weighing AlCl with calculated amount according to the proportion that the mass fraction of oxides in the desulfurizer is 12 percent3Preparing 0.6mol/L salt solution, and then dropwise adding 20% of diethanolamine solution into the salt solution under the conditions that the water bath temperature is 60 ℃ and the stirring speed is 400r/min, wherein the salt-base ratio is 1: 2.5; continuing to stir for 1h under heat preservation after the dropwise addition is finished, then stopping stirring and heating, and aging for 24h to obtain alumina sol; slowly pouring the aluminum sol into the copper-zinc composite oxide precipitate, stirring for 1h at the rotating speed of 600r/min in a water bath at the temperature of 60 ℃, stopping reaction, performing suction filtration, washing with clear water, naturally drying, completely oxidizing, and grinding into powder to obtain desulfurizer raw powder S;
respectively weighing diaspore and kaolin as adhesives according to the proportion of 5% and 4% of the mass fraction of the desulfurizer, simultaneously weighing copper powder and nickel powder as cocatalyst according to the proportion of 0.5% and 3.5% of the mass fraction of the desulfurizer, uniformly mixing the cocatalysts with the desulfurizer raw powder S, adding water, kneading for 30min, tabletting and molding by using a hydraulic press, naturally airing at room temperature, curing, then placing in a drying room, and drying and activating at 240 ℃ in a nitrogen atmosphere to obtain the finished product desulfurizer.
Test examples
The test examples were used to evaluate the physicochemical properties and desulfurization activity of the room-temperature liquid hydrocarbon desulfurization agents obtained in examples 1 to 4, and the evaluation results are shown in table 2.
1. Main physical and chemical performance indexes of normal-temperature liquid hydrocarbon desulfurizing agent and application and operation conditions
Table 1: physical and chemical indexes and operating conditions of normal-temperature liquid hydrocarbon desulfurizing agent
2. Test conditions
Raw materials and reagents are petroleum ether (90-120 ℃), sublimed sulfur, methyl mercaptan, methyl sulfide and silver nitrate, and the chemical reagents are analytically pure;
simulating an oil sample: the active sulfide and petroleum ether are prepared according to a certain proportion.
(1) Elemental sulfur: a small amount of sublimed sulfur is accurately weighed, fully dissolved in petroleum ether, diluted to a certain mass fraction and used as soon as possible in a short time.
(2) Hydrogen sulfide: hydrogen sulfide is a colorless, odorous, acidic gas that is more soluble in hydrocarbons. A specified amount of hydrogen sulfide gas is taken out from a steel cylinder by using a standard gas sampling bag, injected into a closed sample tank filled with petroleum ether, shaken to fully dissolve the hydrogen sulfide, and then diluted to a certain mass fraction.
(3) Thiols and thioethers: preparing standard gas (nitrogen is used as diluent gas) containing mercaptan and thioether with a certain concentration by adopting a professional method, taking a specified amount of gas containing thioether and mercaptan from a steel cylinder by using a standard gas sampling bag, injecting the gas into a closed sample tank filled with petroleum ether, shaking to fully dissolve sulfide, and then diluting to a certain mass fraction.
(4) And calibrating sulfides in the configured oil sample by adopting a sulfur special chromatogram and a sulfur-chlorine microcoulomb meter.
The test conditions are as follows:
in the test, an oil sample with a composition similar to an industrial actual composition is used as an evaluation sample, the total sulfur in a sulfur-containing simulation oil sample for evaluation is controlled to be below 500ppm, and the liquid airspeed is 0.5-10 h-1And the desulfurization environment temperature is 15-60 ℃. And crushing and sieving the prepared desulfurizer to obtain 20-40-mesh small particles, uniformly filling the small particles into a fixed bed microreactor, controlling the height-diameter ratio of a catalyst bed layer to be 3-8, and respectively paving a layer of quartz sand on the upper part and the bottom part of the desulfurizer to serve as a support. The desulfurizing agent evaluation flow chart is shown in the attached figure 2 in detail.
In the evaluation process, the sulfur content and the sulfur form in inlet gas and outlet gas are analyzed by adopting a sulfur special chromatogram and a sulfur-chlorine microcoulomb meter.
The sulfur capacity detection method comprises the following steps: performed with reference to standard HG/T2513;
the copper sheet corrosion detection method comprises the following steps: performed with reference to SH/T0232;
the method for measuring the corrosion of the jet fuel silver sheet comprises the following steps: performed with reference to SH/T0023;
other physical and chemical indexes are executed according to corresponding national standards or line standards.
3. Example evaluation results:
under the test conditions, the normal temperature liquid hydrocarbon desulfurizer samples S prepared under different conditions in examples 1 to 4 were used1-4The basic physicochemical properties, desulfurization performance and metal corrosion performance were evaluated under the evaluation flow of fig. 2, and the evaluation results are shown in table 2:
table 2: desulfurizing agent sample S1-4Evaluation of test results
From the test evaluation results, in the operation interval of the preparation scheme of the normal-temperature liquid hydrocarbon desulfurizer, the normal-temperature liquid hydrocarbon desulfurizer with good activity can be prepared by changing some condition parameters in the preparation process of the desulfurizer, the technical performance parameters meet the index requirements in table 1, and the copper sheet corrosion and silver sheet corrosion tests can meet the technical requirements of the existing industry. Meanwhile, as can be seen from Table 2, sample S3And sample S4The effect in the case of silver flake corrosion is slightly worse than that of sample S1And sample S2The reason is mainly because the concentration and the addition amount of the precipitant in the former are high, and the stirring speed is high, which is not favorable for the dispersion of metal ions and the formation of developed pore structure. At the same time, sample S3And sample S4The addition amount of the copper powder as the medium promoter is low, so that the interception capability of the copper powder on active element sulfur in oil products is weakened, and the corrosion of silver sheets is grade 1.
Compared with the prior art, the invention has the beneficial effects that:
according to the normal-temperature liquid hydrocarbon desulfurizer provided by the invention, hydrogen sulfide is removed by using oxidation state metal, and element sulfur and mercaptan are removed by using reduction state metal, so that sulfides in various forms in oil products are removed to a lower level, and the copper sheet corrosion qualification and the silver sheet corrosion qualification of the oil products are ensured;
according to the preparation method of the normal-temperature liquid hydrocarbon desulfurizer, the aluminum colloid carrier and the active composite oxide are independently prepared, so that the properties of active components and the integrity of a pore channel of the aluminum colloid carrier are favorably ensured; compared with a blending method, the co-precipitation method has the advantages that the co-precipitation method is adopted to prepare the active component and the mixed precipitation method is more exquisite in operation, the prepared active particles are smaller in diameter, the active centers are more dispersed, the pore channel structures are 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.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
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.
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Denomination of invention: A normal temperature liquid hydrocarbon desulfurizer and its preparation method Effective date of registration: 20230217 Granted publication date: 20221004 Pledgee: Bank of China Limited Wuhan Donghu New Technology Development Zone Branch Pledgor: HUBEI HUABANG CHEMICAL Co.,Ltd. Registration number: Y2023420000056 |