阅读说明：本技术 一种深度净化精脱硫剂及其制备方法 (Deep purification fine desulfurizer and preparation method thereof ) 是由 单红飞 赵素云 景云峰 陈玲玲 迟莹 赵宇轩 廖奕鸥 刘聪 李晓凡 孙亮 于 2019-07-26 设计创作，主要内容包括：本发明属于脱硫剂制备技术领域,具体涉及一种深度净化精脱硫剂及其制备方法。该脱硫剂包括锗、锡、铋、锑金属元素或其氧化物中的至少一种,氧化铝,纳米氧化锌,过渡金属氧化物,碱金属或碱土金属化合物,镧系金属或其氧化物,该脱硫剂可以在空速为16000h<Sup>-1</Sup>、温度40℃的条件下对合成气中的有机硫和无机硫进行脱除,使合成气中有机硫和无机硫的总量从20ppm降低至3ppb,脱硫效果好、活性高。此外,该方法工艺简单、制备周期短、能耗低,在实际生产中易操作、实施,且该方法制备得到的脱硫剂可以同时脱除有机硫和无机硫。(The invention belongs to the technical field of desulfurizer preparation, and particularly relates to a deep purification fine desulfurizer and a preparation method thereof. The desulfurizer comprises at least one of germanium, tin, bismuth and antimony metal elements or oxides thereof, aluminum oxide, nano zinc oxide, transition metal oxides, alkali metal or alkaline earth metal compounds, lanthanide series metal or oxides thereof, and can be used at a space velocity of 16000h ‑1 and organic sulfur and inorganic sulfur in the synthesis gas are removed under the condition of 40 ℃, so that the total amount of the organic sulfur and the inorganic sulfur in the synthesis gas is reduced from 20ppm to 3ppb, and the desulfurization effect is good and the activity is high. In addition, the method has simple process, short preparation period and low energy consumption, is easy to operate and implement in actual production, and the desulfurizer prepared by the method can simultaneously remove organic sulfur and inorganic sulfur.)

1. A deep purification fine desulfurizer is characterized by comprising,

2. The deep purification fine desulfurization agent according to claim 1, wherein the particle size of said zinc oxide is not more than 10 nm.

3. The deep purification fine desulfurization agent according to claim 1 or 2, further comprising 10 to 30 parts of a binder;

the adhesive is silica sol or hydroxymethyl cellulose.

4. A process for preparing the deep purifying fine desulfurizing agent as claimed in any one of claims 1 to 3, which comprises,

And (3) fully kneading the components except the binder, adding the binder, mixing, grinding, molding, drying and roasting to obtain the deep purification fine desulfurizer.

5. The preparation method according to claim 4, wherein the nano zinc oxide is prepared by adding a precipitant into zinc salt, adjusting pH to 3-7, adding a surfactant for sufficient reaction, washing, filtering, and drying to obtain the nano zinc oxide.

6. the preparation method according to claim 5, wherein the mass ratio of the zinc salt to the precipitating agent to the surfactant is 1.52-3.55: 1.0-1.2: 0.71-1.49.

7. The method according to claim 5 or 6, wherein the precipitant is added at a rate of 3 to 5 ml/min.

8. The method according to claim 4, wherein the kneading time is 40 to 60 min.

9. The preparation method according to claim 4, wherein the drying temperature is 110-120 ℃ and the drying time is 1.5-2.5 h;

The roasting temperature is 300-400 ℃, and the roasting time is 1.5-2.5 h.

10. Use of the deep purification fine desulfurizing agent according to any one of claims 1 to 3 or the deep purification fine desulfurizing agent prepared by the method according to any one of claims 4 to 9 in the preparation of synthesis gas from coal.

Technical Field

The invention belongs to the technical field of desulfurizer preparation, and particularly relates to a deep purification fine desulfurizer and a preparation method thereof.

Background

The clean conversion and high-efficiency utilization technology of coal resources is an important energy utilization technology for economic, social sustainable development and environmental friendliness in China, wherein a coal gas production process is taken as one of clean coal technologies with the highest coal conversion efficiency, and power generation by utilizing a gas turbine after gasification is one of important ways for clean and high-efficiency utilization of coal. Besides conventional H contained in coal gas₂、N₂、CO、CO₂Besides the components, the catalyst also contains sulfide, and the existence of the sulfide can corrode equipment and pipelines, cause catalyst poisoning in subsequent conversion, reforming and synthesis processes, and seriously pollute the environment after being discharged into the atmosphere. The sulfides mainly present in the synthesis gas are carbonyl sulfide (COS) and H₂S, wherein H₂S is a typical representative of sulfur-containing compound malodorous pollutants, colorless transparent gas has a smelly egg flavor, has strong irritation to a human body, is difficult to dissolve in water, is easy to dissolve in an organic solvent, has a simpler carbonyl sulfide molecular structure, belongs to a linear molecular structure, is connected with each other by double bonds between oxygen atoms and carbon atoms, has special and stable physicochemical properties, and is more difficult to remove carbonyl sulfide than hydrogen sulfide in the deep purification process of synthesis gas, so that the removal of COS is a key for realizing gas fine desulfurization, and the total sulfur of industrial gas can be reduced to the use requirement only by solving the removal of COS.

At present, the most common desulfurization method at home and abroad is a low-temperature catalytic hydrolysis method, and the method needs to remove H in advance₂Catalytic hydrolysis of S, COS to H₂s, fine removal of H₂S, etc. three-step methodThe removal is commonly known as the "sandwich" or "sandwich cake" method. The method has the disadvantages of H₂S has poisoning effect on hydrolysis catalyst and must be pre-removed, and H generated after COS is hydrolyzed₂S is further removed so that only H₂S removal is carried out in two parts and the hydrolysis process is carried out on H₂The concentration of O, oxygen and COS is strictly required and slightly exceeds, the activity of the desulfurizer is linearly reduced, and the method has the advantages of complex process, high cost and long flow.

removing H at home and abroad₂The treatment technique of S can be divided into wet-type and dry-type desulfurization, the former is mainly used for high-concentration H₂Removing S gas; the latter for low concentrations of H₂And (4) removing S gas. In recent years, the method aims at removing H by a dry method₂The research on S gas is relatively more, and different desulfurizing agents and desulfurization process conditions are mainly researched.

Chinese patent document CN107684819A discloses a composite iron-based desulfurizer and a preparation method and application thereof. The composite iron system desulfurizer comprises the following raw materials in parts by weight: 60-80 parts of iron oxyhydroxide, 20-40 parts of basic zinc carbonate and 0.5-1.2 parts of binder. The composite iron system desulfurizer has high specific surface area, can be fully contacted with hydrogen sulfide, can be applied to gas desulfurization under the condition of high space velocity, and has high desulfurization precision and high desulfurization efficiency. Chinese patent document CN106268215A discloses a desulfurizing agent, which is prepared by mixing raw materials of ferric oxide, ferrous sulfate, fluorite and magnesium chloride, adding sodium borate and poly (butylene succinate), and carrying out the steps of curing, drying, roasting and the like. The desulfurizing agents disclosed in the two patents can only remove hydrogen sulfide and achieve higher desulfurization precision, but do not have conversion and adsorption capacity for carbonyl sulfide in organic sulfur.

Chinese patent document CN103212389B discloses a method for preparing a gas fine desulfurization adsorbent by petroleum coke, which comprises the steps of crushing the petroleum coke into 50-100 meshes, and sieving 40-50% of the petroleum coke with a 100-mesh sieve; putting the mixture into a muffle furnace to heat the mixture to 100-200 ℃; adding a chemical activator, an activation aid, a binder, a bonding aid and water for kneading, and extruding into a columnar strip with the diameter of 3-3.5mm and the length of 3-5mm by a screw extruder; petroleum coke powder, chemical activator, activating agent, binder, bonding agent and water in a weight ratio of 1:0.5-3:0-0.2:0.2-0.8:0.02-0.08: 0.3-0.6; naturally drying, and carrying out carbonization and activation treatment; the absorbent disclosed by the invention is low in cost, high in sulfur capacity and strong in organic sulfur treatment capacity, can be used for removing various sulfur and nitrogen containing compounds, improves the comprehensive utilization value of petroleum coke, can be incinerated finally, does not discharge alkali liquor, and is beneficial to environmental protection.

Chinese patent document CN106179328B discloses a deep purification fine desulfurizer comprising ZnAl₂O₄Metal oxide and alkali metal hydroxide or carbonate, wherein the metal oxide is at least one of manganese dioxide, lead oxide and molybdenum trioxide, and the desulfurizing agent can simultaneously remove COS and H₂S, and reach COS and H₂deep purification of S to obtain COS and H in synthetic gas₂The total amount of S is reduced from 50ppb to 5ppb, but the desulfurizing agent is difficult to reduce the high-content sulfur to 5ppb, the sulfur content in the synthesis gas is difficult to further reduce, the temperature of the desulfurizing agent during desulfurization is high, and if the desulfurization temperature is reduced, the space velocity is correspondingly reduced, and the desulfurization activity is deteriorated.

Disclosure of Invention

Therefore, the technical problem to be solved by the invention is to overcome the defects of high desulfurization temperature of the desulfurizer, difficult reduction of sulfur content in synthesis gas and the like in the prior art, thereby providing the deep purification fine desulfurizer and the preparation method thereof.

Therefore, the invention provides the following technical scheme.

The invention provides a deep purification fine desulfurizer, which comprises,

The particle size of the zinc oxide is not more than 10 nm.

The desulfurizer also comprises 10-30 parts of binder;

The adhesive is silica sol or hydroxymethyl cellulose.

The invention also provides a preparation method of the deep purification fine desulfurizer, which comprises the following steps,

and (3) fully kneading the components except the binder, adding the binder, mixing, grinding, molding, drying and roasting to obtain the deep purification fine desulfurizer.

the preparation method of the nano zinc oxide comprises the steps of adding a precipitator into zinc salt, adjusting the pH value to 3-7, adding a surfactant for full reaction, washing, filtering, and drying to obtain the nano zinc oxide.

The mass ratio of the zinc salt to the precipitating agent to the surfactant is 1.52-3.55: 1.0-1.2: 0.71-1.49.

The precipitant is one or more of sodium carbonate, sodium bicarbonate and the like, and the surfactant is one or more of cetyl trimethyl ammonium bromide, sodium linear alkyl benzene sulfonate, sodium lauryl sulfate and the like;

The addition rate of the precipitant is 3-5 ml/min.

The kneading time is 40-60 min.

The drying temperature is 110-120 ℃, and the drying time is 1.5-2.5 h;

The roasting temperature is 300-400 ℃, and the roasting time is 1.5-2.5 h.

The invention also provides an application of the deep purification fine desulfurizer or the deep purification fine desulfurizer prepared by the method in preparation of synthesis gas from coal.

The technical scheme of the invention has the following advantages:

1. The deep purification fine desulfurizer provided by the invention comprises at least one of germanium, tin, bismuth and antimony metal elements or oxides thereof, aluminum oxide, nano zinc oxide, transition metal oxides, alkali metal or alkaline earth metal compounds, lanthanide metal or oxides thereof; the desulfurizing agent can be used at an airspeed of 16000h^-1The organic sulfur and the inorganic sulfur in the synthesis gas are removed under the condition of 40 ℃, so that the total amount of the organic sulfur and the inorganic sulfur in the synthesis gas is reduced from 20ppm to 3ppb, the desulfurization effect is good, and the activity is high；

alkali metal or alkaline earth metal compounds, germanium, tin, bismuth and antimony metal elements or oxides thereof in the desulfurizer can be uniformly distributed in pore channels of zinc oxide and aluminum oxide and attached to the surfaces of the pore channels to provide active centers for hydrolysis and conversion of carbonyl sulfide in organic sulfur, the organic sulfur and the carbonyl sulfide in synthesis gas can be removed under the condition of normal temperature, the carbonyl sulfide and water in the synthesis gas are subjected to hydrolysis reaction to generate hydrogen sulfide and carbon dioxide, the active centers have high reaction rate with the organic sulfur and high hydrolysis reaction efficiency, and the alkaline centers absorb hydrolysate hydrogen sulfide to facilitate the hydrolysis balance of the carbonyl sulfide to be carried out rightwards, increase the hydrolysis rate of the carbonyl sulfide and achieve the purpose of deep purification and desulfurization;

The transition metal oxide in the desulfurizer has a large number of empty tracks and can enter zinc oxide crystal lattices to enhance the interaction force between the transition metal and the zinc oxide, so that the zinc oxide has crystal defects and unbalanced electron distribution, the alkaline site on the surface of the desulfurizer is further enhanced, and the removal of carbonyl sulfide and hydrogen sulfide is facilitated;

Lanthanide series metal or oxides thereof in the desulfurizer belong to a hexagonal system, can form lattice doping with alkali metal or alkaline earth metal, and has nonuniform electron distribution, so that more alkaline active centers are exposed on the surface of the desulfurizer, full-space, half-full and other orbits exist in outer orbits of the lanthanide series metal, sulfur in sulfide has lone pair electrons, and the sulfur is beneficial to conversion of organic sulfur and removal of inorganic sulfur after the lanthanide series is added into the desulfurizer;

the desulfurizer also has good removal effect on thiophene, mercaptan and the like in organic sulfur.

2. According to the deep purification fine desulfurizer provided by the invention, the particle size of zinc oxide is controlled to be below 10nm, so that organic sulfur and inorganic sulfur are favorably diffused on the surface of the desulfurizer, and more desulfurization active sites are exposed on the surface of the desulfurizer, so that the reaction of the zinc oxide and hydrogen sulfide is more sufficient; in addition, the thickness of the vulcanization product wrapped on the outer surface of the crystal grain can be effectively reduced by controlling the grain size of the zinc oxide, the area of a reaction section is increased, and the desulfurization precision and the sulfur capacity of the desulfurizer are improved.

3. The deep purification fine desulfurizer preparation method provided by the invention has the advantages that the components are sequentially subjected to kneading, mixing and grinding, molding, drying and roasting to obtain the desulfurizer, the method is simple in process, short in preparation period and low in energy consumption, and is easy to operate and implement in actual production, and the desulfurizer prepared by the method can simultaneously remove organic sulfur and inorganic sulfur.

4. The preparation method of the deep purification fine desulfurizer provided by the invention can slow the growth speed of zinc oxide grains by controlling the adding rate of the precipitator to be 3-5ml/min when preparing the nano zinc oxide, and the grain size of the nano zinc oxide reaches below 10nm after the surfactant is added on the basis, and the nano zinc oxide is uniformly dispersed, and meanwhile, the specific surface area of the nano zinc oxide is large and can reach 70m²More than g, the organic sulfur and the inorganic sulfur are favorably diffused on the surface of the desulfurizer, so that more desulfurization active sites are exposed to the surface of the desulfurizer.

Detailed Description

The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.