CN113813988A - Preparation method of high-efficiency microcrystalline molecular sieve catalyst for fine desulfurization - Google Patents
Preparation method of high-efficiency microcrystalline molecular sieve catalyst for fine desulfurization Download PDFInfo
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- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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Abstract
The invention relates to a preparation method of a high-efficiency microcrystalline molecular sieve catalyst for fine desulfurization, belonging to the technical field of fine desulfurization in the industries of coke oven gas, blast furnace gas, natural gas and coal chemical industry. The preparation method of the high-efficiency microcrystalline molecular sieve catalyst for fine desulfurization is characterized in that the high-efficiency microcrystalline molecular sieve catalyst comprises a carrier and a nano microcrystalline material; the carrier includes: zeolite materials, high silicon materials; the preparation raw materials of the nano microcrystalline material comprise: silicate raw materials, a crystal nucleus agent, a clarifying agent, a pore-increasing agent and an activating agent; the zeolite material includes: calcium X type material, ZSM-5 material, HY raw material, and white clay.
Description
Technical Field
The invention relates to the technical field of fine desulfurization in coke oven gas, blast furnace gas, natural gas and coal chemical industry, in particular to a preparation method of a high-efficiency microcrystalline molecular sieve catalyst for fine desulfurization.
Background
The fuel gas used by the heating furnace and the boiler in the steel industry mainly comes from coke oven gas produced by coking and blast furnace gas produced by blast furnace smelting. The coke oven gas is from high temperature dry distillation gas of coal and contains 55-60 parts of H223-27 parts of CH45-8 parts of CO and 2-4 parts of CnHm1.5-3 parts of CO20.3-0.8 part of O23-7 parts of N2In addition, it also contains a certain quantity of H2S and organic sulfur (carbon disulfide, carbon oxysulfide, thiol, thioether, thiophene, methyl thiol, methyl sulfide, etc.), and water vapor, naphthalene, tar, benzene, ammonia, hydrogen cyanide, etc.; blast furnace gas contains 1.5-3.0 parts of H20.2-0.5 part of CH425-30 parts of CO and 9-12 parts of CO255-60 parts of N20.2-0.4 part of O2Also contains 30-60mg/Nm3H2S and 80-150mg/Nm3Organic sulfur (carbonyl sulfide, carbon disulfide, mercaptans, and thioethers), dust, and the like. The existing coke oven gas desulfurization technology mainly removes inorganic sulfur, and organic sulfur removal is rarely considered, SO that even if the content of hydrogen sulfide is less than 20mg/m3, the standard emission of flue gas SO2 after gas combustion is difficult to ensure; blast furnace gas was not removed due to the low H2S content. The hydrogen sulfide in the coke oven gas is removed by a plurality of methods, the method is commonly used in China at present by vacuum carbonate, AS, HPF and PDS methods, and the content of the hydrogen sulfide in the gas after the desulfurizing tower is generally less than or equal to 300mg/Nm3The content of organic sulfur is no more than 350mg/Nm3. In order to implement the ultra-low emission standard of the atmospheric pollutants in the steel industry and implement source treatment, the heated gas in the industrial furnace needs to be subjected to fine desulfurization or deep desulfurization, namely organic sulfur removal.
The relatively mature method for removing organic sulfur is catalytic hydroconversion, and the basic process route is the hydroconversion of organic sulfur in coal gas into hydrogen sulfide → absorption of ferro-manganese desulfurizer → fine desulfurization of zinc oxide, and the process has high desulfurization precision, but also has high operation cost, long process route and undesirable removal of thiophene. At present, the method for removing organic sulfur in coal gas tends to a molecular sieve/microcrystal adsorption + hydrogenolysis/hydrolysis process, but tar, naphthalene and dust in the coal gas easily cause adsorbent blockage, and hydrogen cyanide easily causes catalyst poisoning.
Disclosure of Invention
Based on the above, the invention aims to provide a preparation method of a high-efficiency microcrystalline molecular sieve catalyst for fine desulfurization, which solves the technical problems that in the prior art, thiophene is not ideal to be removed, and an adsorbent is easy to block, so that catalyst poisoning is easy to cause.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a preparation method of a high-efficiency microcrystalline molecular sieve catalyst for fine desulfurization, which is characterized in that the high-efficiency microcrystalline molecular sieve catalyst comprises a carrier and a nano microcrystalline material;
the carrier includes: zeolite materials, high silicon materials;
the preparation raw materials of the nano microcrystalline material comprise: silicate raw materials, a crystal nucleus agent, a clarifying agent, a pore-increasing agent and an activating agent;
the zeolite material includes: calcium X type material, ZSM-5 material, HY raw material and white clay;
the nano-scale microcrystalline material, the high silicon material and the two zeolite materials are first active components; mineral material adhesive, organic fiber adhesive and other two zeolite materials are used as second active components;
the preparation method of the high-efficiency microcrystalline molecular sieve catalyst comprises the following steps:
s1, taking zeolite material as a carrier of molecular sieve raw material, and putting 40-60 parts of high silicon material into a mother liquor pool for high-temperature deep exchange;
s2 is steamed for 3-10h at 130 ℃ in a microwave line 115-32 after the high-temperature deep exchange in the step S1 to obtain the high-silicon zeolite material;
s3, adding 20-35 parts of nano microcrystalline material into the high-silicon zeolite material obtained in the step S2 for cooking exchange;
s4 is processed by cooking and exchanging in step S3 to prepare the shaping.
The nanocrystalline material in the step S3 is prepared from 8-20 parts of a crystal nucleating agent, 2-10 parts of a pore-increasing agent, 5-24 parts of an active component and a clarifying agent by heating and activating at 380 ℃ in a medium temperature furnace for 2-7 h.
Preferably, step 4 is specifically:
steaming and exchanging in step S3 to obtain cylindrical clover-shaped or spherical particles with particle size of 1.6-2.5 mm.
Preferably, the preparation of the high-efficiency microcrystalline molecular sieve catalyst comprises the following steps:
s11 respectively exchanging 6-15 parts of calcium X-type material, 13-26 parts of ZSM-5 material, 12-20 parts of HY raw material, 3-8 parts of white clay and 40-60 parts of microcrystalline cellulose for later use to obtain high-silicon zeolite material;
s12, taking 40-60 parts of nano microcrystalline material, adding 1.2-1.8 parts of pore-increasing agent and acid for later use, wherein the acid is one of oxalic acid and citric acid;
s13 taking 2.5-5.5 parts of SG sesbania plant gum and 3-8 parts of hydroxypropyl methyl cellulose for later use;
s14, taking 3-7 parts of water glass or 0.05-0.35 part of nitric acid for later use, and weighing 15-22 parts of water for later use;
s15, putting the materials of S11, S12 and S13 into a kneader in sequence, mixing and kneading for 20 minutes, putting the material of S14, uniformly mixing and kneading for 40 minutes, discharging the slurry, putting the slurry into a strip extruding machine, extruding the strips by a clover or clover mould, airing, drying and roasting at high temperature to obtain the microcrystalline molecular sieve.
Preferably, the microcrystalline cellulose is microcrystalline cellulose MCC powder.
Preferably, the preparation of the high-efficiency microcrystalline molecular sieve catalyst comprises the following steps:
s111, exchanging 6-15 parts of calcium X-type raw material, 13-26 parts of ZSM-5 raw material, 13-20 parts of HY raw material, 3-8 parts of white clay and 4-9 parts of microcrystalline cellulose for later use;
s112, adding 47-56 parts of nano-scale efficient microcrystalline material into 8-15 parts of pore-increasing agent and acid for later use, wherein the acid is one of oxalic acid and citric acid;
s113 taking 2.3-4.2 parts of sesbania powder or 3.2-7.8 parts of hydroxypropyl methyl cellulose for later use;
s114, weighing 17-23 parts of water, 4.5-7.5 parts of water glass and 0.12-0.33 part of nitric acid liquid for later use according to the weight of the total raw materials of the batch;
s115, sequentially putting the materials for standby in S111, S112 and S113 into a kneader, mixing the dry powder materials for 12-18 minutes, adding 17-23 parts of water in S114, uniformly mixing for 43-58 minutes, discharging the slurry, and conveying into a vacuum machine for steaming for 50-72 minutes; then putting the slurry into an extrusion honeycomb molecular sieve platform, extruding a honeycomb molecular sieve blank with the size of 100 multiplied by (50-300) through a mould by an air compressor with the weight of 80-120kg, quickly sending the honeycomb molecular sieve blank into a microwave line, drying the honeycomb molecular sieve blank at the microwave temperature of 103 plus materials and 125 ℃ to obtain a honeycomb molecular sieve semi-finished product, and roasting the honeycomb molecular sieve semi-finished product at the high temperature of 525 plus materials and 630 ℃ after 5-7 hours to obtain a honeycomb molecular sieve product.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a high-efficiency microcrystalline molecular sieve catalyst, which is characterized in that a nano microcrystalline material, a high silicon material and two zeolite raw materials are used as first active components, wherein a mineral material adhesive, an organic fiber adhesive and the other two zeolite raw materials are used as second active components, and the stability and the using effect of the microcrystalline molecular sieve catalyst are improved under the condition of good surface activity.
The applicant shows the proposal:
the invention provides a high-efficiency microcrystal fine desulfurization molecular sieve catalyst, which takes the adverse effects that the service life of the currently used common microcrystal molecular sieve is short and the regeneration period is gradually prolonged into consideration. The high-efficiency microcrystalline molecular sieve is promoted to be used as a carrier, then a noble metal with strong activity or a special molecular sieve raw material is loaded, and the formula structure of the molecular sieve is improved, so that the process conditions of dewatering, adsorption and desorption are realized, and the operation effect is accurately controlled.
The composite carrier of the high-efficiency microcrystalline molecular sieve catalyst comprises a zeolite raw material, a high-silicon-content raw material and a Hy raw material. The nano microcrystalline material is composed of the specific formula, wherein the nano microcrystalline material is composed of crystals of structural units such as a silicate raw material, an organic chemical raw material, a crystal nucleating agent, a clarifying agent, an additive, a pore-increasing agent, an active agent and the like.
The high-efficiency microcrystalline molecular sieve is mainly embodied as an adsorbent, a desorbent and a catalyst. The active components in the composite carrier comprise trace noble metal, various zeolite raw powders, high-efficiency microcrystalline materials and the like. The product of the invention adopts microcrystalline cellulose MCC powder, and the product has the effects of various components such as an anticaking agent, an adsorbent, a binder and the like, fully exerts the activity and catalytic performance of the microcrystalline molecular sieve catalyst and also improves the main performance of the product.
The material and the filling material of the invention are different, the processes of rough desulfurization and fine desulfurization are different, and the fine desulfurization effect can be further improved by selecting high-efficiency microcrystalline materials. The high-efficiency microcrystalline molecular sieve is prepared by compounding 40-65% of high-silicon zeolite material, 25-35% of microcrystalline material, 15-25% of microcrystalline cellulose and the like.
In another aspect of the invention, the high-efficiency microcrystalline molecular sieve catalyst is prepared by attaching active metal components to pores of a molecular sieve by using a composite carrier of the high-efficiency microcrystalline molecular sieve through an impregnation method.
The fine desulfurization process of the invention adopts the principle of circular desulfurization to convert organic sulfur into hydrogen sulfide. Coke oven gas H from crude desulfurization2S content is less than or equal to 300mg/Nm3The content of organic sulfur is no more than 350mg/Nm3After being conveyed to a fine desulfurization equipment area by a pipeline, the total sulfur content in the coal gas is reduced to 10mg/m by adsorption, hydrolysis and desorption in a fine desulfurization tower3The following; and (4) returning the impurities such as hydrogen sulfide, aromatic hydrocarbon and the like desorbed by regeneration to the crude desulfurization device, and entering a circulating desulfurization process route.
The preparation process of the high-efficiency microcrystalline molecular sieve catalyst selects various modes: the honeycomb type honeycomb molecular sieve has the advantages that the honeycomb type honeycomb body is 100 x (50-300) mm, the clover shape is 3-5 x 8-20mm, the spherical shape is 3-5mm, and the column shape is (1.5-1.7) x (6-20) mm, the use effect of the honeycomb type honeycomb molecular sieve is that the honeycomb type is larger than the clover shape, the spherical shape and the column shape have overlarge density, the smoke flow rate is slow, the honeycomb type is good, but the treatment of a scrapped honeycomb molecular sieve is difficult, so the honeycomb type, the clover shape or the clover shape are matched according to the proportion, the use effect is the best, and the matching proportion is 30-70 percent respectively.
The high-efficiency microcrystal molecular sieve catalyst for fine desulfurization is mainly used for adsorbing H in coke oven gas2S, various organic sulfur, naphthalene, tar, ammonia, HCN and other impurity components enter from the bottom of the adsorption tower, and clean coal gas is discharged from the top and enters a main pipe network to be supplied to downstream users for use.
After the adsorption tower reaches the saturation degree, 3000-5000Nm coke oven gas pipe network is used for extracting the coke oven gas3The clean coke oven gas of/h is used as regeneration desorption gas. The regeneration gas is generally 280-320 ℃, the single-tower regeneration time is about 40-60H, and the gas is rich in H2And (4) returning desorption gas of impurities such as S, naphthalene, tar, ammonia, HCN and the like to the crude desulfurization system.
The zeolite raw material of the refined desulfurization molecular sieve catalyst is from natural zeolite or artificial zeolite, four zeolite materials of the zeolite raw material are used as carriers of the molecular sieve raw material, then 60% of high silicon material is put into a mother liquor pool for high-temperature deep exchange, and then the mother liquor is steamed for 3-10h at the temperature of 130 ℃ in a microwave line of 115-. Adding 20-30% of nano microcrystalline material into the steamed powder, such as (8-20% of crystal nucleus agent, 2-10% of pore-increasing agent and 5-24% of active component), and heating and activating for 2-7h at 380 ℃ by a medium temperature furnace to obtain the microcrystalline material. In order to better achieve the process effect of adsorption and desorption, 8-20% of HY raw material and 15-28% of ZSM-5 raw material which are prepared in advance are subjected to cooking exchange to prepare the required columnar clover shape or spherical particle shape of 1.6-2.5 mm. (the microcrystalline material is mainly silicon carbide and quartz sand which react at a certain temperature to form a nitride microcrystalline structure), and the microcrystalline material has good heating conditions:
1. under the interaction condition of high temperature of 800 ℃ or low temperature quick heating and quenching below 120 ℃, no destructive effect exists, and the molecular sieve can be used as usual under the alternate environment of partial acid or partial alkali in the operation process.
2. The effective adsorption pore space of the microcrystalline molecular sieve is 30-40% larger than that of the common molecular sieve, and the crushing strength is about 130-150N, which is higher than the crushing rate of the common molecular sieve by more than 28%.
3. Application of microcrystalline molecular sieve to H2S, hydrogen cyanide and other toxic gases have strong anti-poisoning performance, and even toxic color spots exist on the surface, the molecular sieve framework still cannot collapse, and the operation cannot be influenced.
4. The microcrystal material has high activity, and the hydrophobic effect reaches over 70 percent, but the microcrystal material contains trace water and H in coke oven gas2S and organic sulfur have good adsorption separation desorption effect.
5. The microcrystalline molecular sieve has reasonable structure, stable operation and H pair2S and organic sulfur ensure efficient separation and desorption of various process indexes.
6. The microcrystalline molecular sieve has four different pore channel structures, can absorb and desorb various harmful gases with different molecular diameters, and has the activity more than 3-5 times that of a common molecular sieve.
7. The microcrystalline nano-grade material creates higher anti-crushing capability for the molecular sieve, the falling powder degree is less than or equal to 0.01 percent wt, the abrasion rate is less than or equal to 0.03 percent wt, and the service life is not less than 5 years.
8. The raw materials for preparing the nano-scale microcrystalline molecular sieve are basically microcrystalline composite zeolite raw materials and microcrystalline fiber materials, so that the high efficiency and environmental protection of the molecular sieve material are ensured, and the repeated regeneration and use effects of the molecular sieve are also ensured.
9. The high-efficiency microcrystalline molecular sieve can be used as an environment-friendly material after being treated after being discarded in service life.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1:
the high-efficiency microcrystalline molecular sieve of example 1 is prepared by exchanging raw materials such as a nano microcrystalline material, microcrystalline cellulose, four kinds of zeolite and the like. 40-60 parts of nano microcrystalline material, 13-26 parts of ZSM-5 raw material, 13-20 parts of HY raw material, 6-15 parts of calcium X raw material and 3-8 parts of white clay, wherein the raw materials are prepared by performing exchange twice and cooking twice according to a proportion, and then the prepared raw materials are granulated and formed.
1) According to the sequence proportion of the raw materials, 6-15 parts of calcium X type material, 13-26 parts of ZSM-5 material, 12-20 parts of HY raw material, 3-8 parts of white clay and 40-60 parts of microcrystalline cellulose are exchanged for later use.
2) Adding pore-increasing agent and oxalic acid or citric acid in 40-60 parts of nano microcrystalline material in a proportion of 1.2-1.8 for later use.
3) Weighing the following components in percentage by weight according to the mixing and kneading ratio of the kneader in one batch: 2.5-5.5 parts of SG sesbania plant gum and 3-8 parts of hydroxypropyl methyl cellulose for later use.
4) According to the weight ratio of one batch of the kneader, 15-22 parts of water, 3-7 parts of water glass or 0.05-0.35 part of nitric acid are weighed for standby.
5) Putting the materials 1), 2) and 3) into a kneader in sequence, mixing and kneading the dry powder materials for 20 minutes, then putting the water and the like in the 4) into the kneader, uniformly mixing and kneading the materials for 40 minutes, then discharging the slurry into a strip extruding machine, extruding the strips by adopting a clover or clover mould, airing, drying and roasting at high temperature to obtain the microcrystalline molecular sieve.
The technical solution of the embodiment is to perform cooking exchange between the carrier raw material and the high-efficiency microcrystalline material in a smokeless, dustless and anhydrous environment, so that the sewage treatment link during aging, filtering or washing at high temperature is eliminated, the activity and the service life of the molecular sieve are ensured, and the preparation time, the labor and the materials are saved.
Example 1 product testing results are given in Table 1 below
TABLE 1
| Product name | Microcrystalline molecular sieve |
| Specification of | φ3-5×8×18mm |
| Appearance of the product | Clover type column |
| Specific surface area | 280-500m2/g |
| Pore volume | 0.3-0.6ml/mg |
| Bulk specific gravity | 620kg/m3 |
| Compressive strength | Not less than 95N/granule |
Example 1 the purified coke oven gas of the product has the following composition contents as shown in Table 2
TABLE 2
Example 2:
the weight ratio and the brand name of the formulation of the microcrystalline molecular sieve of the invention and the formulation of example 1 are the same.
Putting the raw materials into a kneader in sequence, mixing and kneading the dry powder materials for 20 minutes, then adding water with the same weight as that in the embodiment 1, uniformly kneading for 40-50 minutes, discharging the slurry, feeding the slurry into a strip extruding machine, extruding strips by adopting a mold as a column, airing, drying and roasting at high temperature to obtain the microcrystalline strip column-shaped molecular sieve.
Example 2 product test results
| Product name | Microcrystalline molecular sieve |
| Specification of | 1/8φ3.1-3.3×8×20mm |
| Appearance of the product | Milky white strip column |
| Specific surface area | 260-500m2/g |
| Pore volume | 0.25-0.5ml/mg |
| Bulk specific gravity | 630kg/m3 |
| Compressive strength | More than or equal to 110N/granule |
Example 2 composition content of purified Coke oven gas
It can be seen from the comparison between example 2 and example 1 that there is no difference in product properties, and the indexes of the composition content after the coke oven gas purification in example 2 are all higher than those in example 1, so that it can be seen that the catalyst is prepared into clover or clover shape, which is better in gas purification effect.
Example 3:
the high-efficiency microcrystalline molecular sieve of example 3 is prepared by weighing several microcrystalline zeolite materials 15-26 parts, nano microcrystalline material 35-45 parts, calcium X material 15-23 parts, and high-silicon microcrystalline material molecular sieve 17-24 parts, dry-mixing in a conical blender for 15 minutes, adding microcrystalline cellulose, clay, and other raw materials, and mechanically granulating the obtained raw powder material in the same manner as in example 1.
1) The technical scheme of the embodiment 3 is that the microcrystalline spherical molecular sieve with the spherical size of 3-5mm is prepared by drying the raw materials in the air, drying at a medium-low temperature and roasting at a high temperature.
2) The ball making process is simple, but the raw material selectivity is strong, and each powder raw material must be screened before production and processing.
3) The spherical molecular sieve is a conventional method of the traditional process, but the operation conditions are relatively wide, mainly considering the use conditions and actual detection results of the molecular sieve.
Example 3 product test results
| Product name | JF-100 microcrystalline molecular sieve |
| Specification of | φ3-5mm |
| Appearance of the product | White in the shape of small ball |
| Specific surface area | 260-500m2/g |
| Pore volume | 025-0.5ml/mg |
| Bulk specific gravity | 640kg/m3 |
| Compressive strength | 148N/particle |
Example 3 composition content of purified Coke oven gas
As can be seen from the comparison of example 3 and example 1, the compressive strength of the product of example 3 is higher than that of example 1, and the coke oven gas purification effect is still better than that of example 1, so that the catalyst prepared in the application has better compressive capacity in a spherical shape but the gas purification effect is not as good as that of clover or clover.
Example 4:
1) the raw material requirements of the microcrystalline honeycomb molecular sieve are very strict. The prior art solution is essentially the same as example 1, with much finer screens of the other raw materials. Firstly, 6-15 parts of calcium X type raw material, 13-26 parts of ZSM-5 raw material, 13-20 parts of HY raw material, 3-8 parts of white clay and 4-9 parts of microcrystalline cellulose are exchanged for later use.
2) Adding 47-56 parts of nano-scale high-efficiency microcrystalline material into 8-15 parts of pore-increasing agent oxalic acid or citric acid for later use.
3) Putting raw materials of a batch into a kneader, and keeping 2.3-4.2 parts of sesbania powder (SG vegetable gum) or 3.2-7.8 parts of hydroxypropyl methyl cellulose for later use.
4) According to the weight of the total raw materials of the batch, 17-23 parts of water, 4.5-7.5 parts of water glass and 0.12-0.33 part of nitric acid liquid are weighed for later use.
5) Putting the materials 1), 2) and 3) into a kneader in sequence, mixing the dry powder materials for 12-18 minutes, then adding 17-23 parts of water 4), uniformly mixing for 43-58 minutes, discharging the slurry, and sending into a vacuum machine for steaming for 50-72 minutes. Then putting the microcrystalline slurry into an extrusion honeycomb molecular sieve platform, extruding a 100 x (50-300) honeycomb molecular sieve blank through a mould by an air compressor of 80-120kg, quickly feeding the blank into a microwave line, drying at the microwave temperature of 103 plus materials and 125 ℃ to obtain a honeycomb molecular sieve semi-finished product, and roasting at the high temperature of 525 plus materials and 630 ℃ after 5-7 hours to obtain a honeycomb molecular sieve product.
Example 4 product test results
| Product name | Microcrystal cellular molecular sieve |
| Specification of | Phi 100X 50 holes |
| Appearance of the product | Cellular shape with small pores |
| Specific surface area | 320-620m2/g |
| Pore volume | 0.3-0.45ml/mg |
| Bulk specific gravity | 580-600kg/m3 |
| Compressive strength | Not less than 130N/block |
Example 4 composition content of purified Coke oven gas
As can be seen from the comparison between the example 4 and the example 1, the specific surface area of the example 4 is larger, the pressure resistance is stronger, the tar, the naphthalene, the ammonia and the HCN are removed more thoroughly after the coke oven gas is purified, the adsorption space velocity is faster, and the gas phase pressure drop is lower.
The high-efficiency microcrystalline molecular sieve of example 4 is a process route for finishing fine desulfurization in coke oven gas, blast furnace gas and coal chemical industry. Because the microcrystalline molecular sieve desorption tower is higher in packing, all columnar molecular sieves such as clover are used, the packing density is higher, the resistance of the air space velocity is increased, the molecular sieves are gradually lost after long-term operation, the water regeneration at the bottom of the adsorption tower is not thorough, the microcrystalline molecular sieves are uneven in adsorption activity, the desulfurization effect of light people is reduced, and the service life of heavy people is limited. In order to improve the smooth space velocity of molecular sieve adsorption and the balanced stress during adsorption and desorption, the microcrystalline molecular sieve is in a segmented modeling structure in the embodiment 4, and adsorption pores are regularly butted in a horizontal and vertical manner, so that the adsorption activity of the microcrystalline honeycomb molecular sieve is improved.
The invention can obtain the effect under the conditions of small test accumulation and pilot test amplification. However, in the explanation of the examples, the duplicate explanation of the grammage and the material ratio is omitted.
The high-efficiency microcrystalline molecular sieve catalyst integrated with various adsorption pore diameters has selective adsorption, desorption and desorption effects.
The high-efficiency microcrystal molecular sieve catalyst normally works at the operating temperature of 30-180 ℃, the regeneration temperature can be selected within the range of 160-350 ℃, and the service life of the molecular sieve can be repeatedly regenerated to reach the service life of 5-7 years according to the crystallinity and the adsorption condition of the microcrystal molecular sieve.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (9)
1. The preparation method of the high-efficiency microcrystalline molecular sieve catalyst for fine desulfurization is characterized in that the high-efficiency microcrystalline molecular sieve catalyst comprises a carrier and a nano microcrystalline material;
the carrier includes: zeolite materials, high silicon materials;
the preparation raw materials of the nano microcrystalline material comprise: silicate raw materials, a crystal nucleus agent, a clarifying agent, a pore-increasing agent and an activating agent;
the zeolite material includes: calcium X type material, ZSM-5 material, HY raw material and white clay;
the nano-scale microcrystalline material, the high silicon material and the zeolite material are first active components; the mineral material adhesive, the organic fiber adhesive and the zeolite material are used as second active components;
the preparation method of the high-efficiency microcrystalline molecular sieve catalyst comprises the following steps:
s1, taking zeolite material as a carrier of molecular sieve raw material, and putting 40-60 parts of high silicon material into a mother liquor pool for high-temperature deep exchange according to parts by weight;
s2 is steamed for 3-10h at 130 ℃ in a microwave line 115-32 after the high-temperature deep exchange in the step S1 to obtain the high-silicon zeolite material;
s3, adding 20-35 parts of nano microcrystalline material into the high-silicon zeolite material obtained in the step S2 for cooking exchange;
s4 is subjected to cooking exchange in the step S3 to prepare and form;
the nanocrystalline material in the step S3 is prepared from 8-20 parts of a crystal nucleating agent, 2-10 parts of a pore-increasing agent, 5-24 parts of an active component and a clarifying agent by heating and activating at 380 ℃ in a medium temperature furnace for 2-7 h.
2. The method according to claim 1, wherein step 4 comprises:
and (5) performing cooking exchange in the step S3 to obtain the columnar clover shape.
3. The method according to claim 1, wherein step 4 comprises: the spherical particles with the particle size of 1.6-2.5mm are prepared after the cooking exchange in the step S3.
4. The method of claim 1, wherein the preparing the high efficiency microcrystalline molecular sieve catalyst comprises the steps of:
s11, respectively exchanging 6-15 parts of calcium X-type material, 13-26 parts of ZSM-5 material, 12-20 parts of HY raw material, 3-8 parts of white clay and 40-60 parts of microcrystalline cellulose according to parts by weight for later use to obtain a high-silicon zeolite material;
s12, taking 40-60 parts of nano microcrystalline material, adding 1.2-1.8 parts of pore-increasing agent and acid for later use, wherein the acid is one of oxalic acid and citric acid;
s13 taking 2.5-5.5 parts of SG sesbania plant gum and 3-8 parts of hydroxypropyl methyl cellulose for later use;
s14, taking 3-7 parts of water glass for later use, and weighing 15-22 parts of water for later use;
s15, putting the materials of S11, S12 and S13 into a kneader in sequence, mixing and kneading for 20 minutes, putting the material of S14, uniformly mixing and kneading for 40 minutes, discharging the slurry, feeding into a strip extruding machine, extruding the strip by a die, airing, drying, and roasting at high temperature to obtain the microcrystalline molecular sieve.
5. The method of claim 4, wherein the preparing the high efficiency microcrystalline molecular sieve catalyst comprises the steps of:
s14 nitric acid 0.05-0.35 part is taken for standby, and water 15-22 parts is weighed for standby.
6. The method of claim 3, wherein the microcrystalline cellulose is microcrystalline cellulose MCC powder.
7. The production method according to claim 1,
s111, exchanging 6-15 parts of calcium X-type raw material, 13-26 parts of ZSM-5 raw material, 13-20 parts of HY raw material, 3-8 parts of white clay and 4-9 parts of microcrystalline cellulose for later use;
s112, adding 47-56 parts of nano-scale efficient microcrystalline material into 8-15 parts of pore-increasing agent and acid for later use, wherein the acid is one of oxalic acid and citric acid;
s113 taking 2.3-4.2 parts of sesbania powder or 3.2-7.8 parts of hydroxypropyl methyl cellulose for later use;
s114, weighing 17-23 parts of water, 4.5-7.5 parts of water glass and 0.12-0.33 part of nitric acid liquid for later use according to the weight of the total raw materials of the batch;
s115, sequentially putting the materials for standby in S111, S112 and S113 into a kneader, mixing the dry powder materials for 12-18 minutes, adding 17-23 parts of water in S114, uniformly mixing for 43-58 minutes, discharging the slurry, and conveying into a vacuum machine for steaming for 50-72 minutes; then putting the slurry into an extrusion honeycomb molecular sieve platform, extruding a honeycomb molecular sieve blank with the size of 100 multiplied by (50-300) through a mould by an air compressor with the weight of 80-120kg, quickly sending the honeycomb molecular sieve blank into a microwave line, drying the honeycomb molecular sieve blank at the microwave temperature of 103 plus materials and 125 ℃ to obtain a honeycomb molecular sieve semi-finished product, and roasting the honeycomb molecular sieve semi-finished product at the high temperature of 525 plus materials and 630 ℃ after 5-7 hours to obtain a honeycomb molecular sieve product.
8. The method according to claim 7, wherein 3.2 to 7.8 parts of hydroxypropylmethylcellulose is taken as the S113 stock solution.
9. The application of the product prepared by the preparation method of any one of claims 1 to 8 as a high-efficiency microcrystalline molecular sieve catalyst for fine desulfurization.
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| CN111334339A (en) * | 2020-03-16 | 2020-06-26 | 山东洲蓝环保科技有限公司 | Fine desulfurization method for blast furnace gas |
| CN111420632A (en) * | 2020-03-30 | 2020-07-17 | 中国石油大学(北京) | Composite molecular sieve, desulfurization adsorbent, preparation method and application thereof |
| CN112246217A (en) * | 2020-10-30 | 2021-01-22 | 上海绿强新材料有限公司 | Integral honeycomb molecular sieve for purifying VOCs (volatile organic compounds) in zeolite adsorption rotating wheel and preparation method thereof |
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| CN111334339A (en) * | 2020-03-16 | 2020-06-26 | 山东洲蓝环保科技有限公司 | Fine desulfurization method for blast furnace gas |
| CN111420632A (en) * | 2020-03-30 | 2020-07-17 | 中国石油大学(北京) | Composite molecular sieve, desulfurization adsorbent, preparation method and application thereof |
| CN112246217A (en) * | 2020-10-30 | 2021-01-22 | 上海绿强新材料有限公司 | Integral honeycomb molecular sieve for purifying VOCs (volatile organic compounds) in zeolite adsorption rotating wheel and preparation method thereof |
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