CN110980763A - Modification method and application of molecular sieve - Google Patents
Modification method and application of molecular sieve Download PDFInfo
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- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- C01B39/10—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the replacing atoms being at least phosphorus atoms
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Abstract
The invention relates to a modification method of a molecular sieve, which comprises the step of adding an organic phosphonic acid ligand on the molecular sieve to combine the molecular sieve with the organic ligand, and can be used in the industrial production of a silicon-aluminum molecular sieve and a titanium-silicon molecular sieve. The invention is obtained by at least the following raw materials: the silicon-aluminum molecular sieve or the titanium-silicon molecular sieve has the silicon-aluminum ratio of preferably 20-35 and the silicon-titanium ratio of preferably 35-50; the organic ligand is organic phosphonic acid with different chain lengths. By adding the organic phosphonic acid ligand, the invention can increase the dispersion degree of the molecular sieve in the oil product, and can effectively solve the problems of low cracking capability, high reaction temperature, high molecular sieve addition amount and the like caused by poor dispersion of the inorganic molecular sieve in the organic oil product in the suspension bed hydrocracking process.
Description
Technical Field
The invention relates to a modification method of a silicon-aluminum molecular sieve or a titanium-silicon molecular sieve, a molecular sieve obtained by modification and application thereof, belonging to the field of petrochemical industry.
Background
The molecular sieve is a kind of crystalline porous inorganic substance whose skeleton is in space network structure, and is made up by using [ AlO4]And [ SiO ]4]The tetrahedral units of (a) are formed by staggering and sharing oxygen atoms. Wherein [ AlO ] is4]The tetrahedral unit exhibits electronegativity and in [ AlO ]4]Cations that balance the framework charge are also present near the tetrahedra to maintain the electroneutrality of the molecular sieve framework. These cations, which balance the electrical neutrality, may be exchanged with other ions by ion exchange, thereby affecting or even altering the performance of the molecular sieve. Due to the structural characteristics, the molecular sieve has three characteristics of catalysis, selective adsorption and ion exchange, and is widely applied to the field of petrochemical industry. In the aspect of hydrocracking, by modifying the molecular sieve and modulating metal ions, the yield of gasoline and the yield of middle distillate oil are continuously improved, the nitrogen resistance of the catalyst is improved, and the operation period is prolonged.
In the existing various heavy oil processing technologies, the suspension bed hydrogenation process has the characteristics of high conversion rate, wide raw material adaptability and the like, and is one of effective ways for deep processing of inferior heavy oil, and the traditional solid powder catalyst is easily inactivated due to pore channel blockage; the water-soluble catalyst is easy to agglomerate in the dehydration process to reduce the activity; the oil-soluble catalyst can well solve the problems, can effectively improve the liquid yield, reduce the gas product and coke rate, and has the greatest prospect in realizing the target of all conversion of residual oil. However, in the prior art, most of oil-soluble catalysts are metal organic complexes such as molybdenum, cobalt, nickel and the like, and mainly the dispersion degree of an inorganic hydrogenation active phase in an oil phase is improved, so that the hydrogenation active phase has higher hydrogenation activity. However, as a catalyst for treating heavy oil in a suspension bed, not only has high hydrogenation activity, but also has strong cracking capability, so that the heavy oil can be cracked into low molecular weight compounds at a lower reaction temperature and simultaneously hydrogenated. Thereby improving the yield of the liquid oil product and reducing the reaction severity.
The traditional molecular sieve is widely applied to hydrocracking treatment of common oil products, but because the composition of the traditional molecular sieve is mainly inorganic aluminosilicate, when the traditional molecular sieve is directly applied to hydrocracking treatment of suspended bed heavy oil, inorganic components cannot be highly dispersed in an organic oil phase and are easy to settle, so that the traditional molecular sieve cannot play a role in efficiently cracking heavy oil macromolecules. Therefore, the invention takes organic phosphonic acid with strong coordination capacity as a ligand to modify and prepare a series of oil-soluble molecular sieve catalysts with different phosphorus-aluminum ratios or phosphorus-titanium ratios. The introduction of the organic phosphonic acid ligand can not only greatly improve the dispersity of the inorganic molecular sieve in an oil phase, but also improve the acidity of the molecular sieve through the introduction of acidic phosphate radicals, so that the molecular sieve has higher cracking performance in the process of treating the suspension bed heavy oil.
Disclosure of Invention
The invention aims to solve the technical problems that in the hydrocracking process of an oil product suspension bed in the prior art, the molecular sieve has poor dispersibility in the oil product and is easy to deposit, so that the cracking effect is reduced, coke is easy to generate, a large amount of solid particles in tail oil are difficult to utilize and treat, and the like.
In order to solve the technical problems, the invention provides a molecular sieve modification method, which comprises the following steps:
dissolving an organic ligand in an organic solvent, uniformly mixing the organic ligand with a molecular sieve or a pretreated molecular sieve, adjusting the pH value to be weakly acidic or neutral through a hydrothermal reaction or a reflux reaction, and then filtering and drying to obtain the oil-soluble molecular sieve.
The molecular sieve can be a molecular sieve with an excellent pore structure and containing metal cations, such as a silicon-aluminum molecular sieve or a titanium-silicon molecular sieve. Including but not limited to MCM series molecular sieve, TS series molecular sieve, ZSM series molecular sieve, Y type molecular sieve, MWW type molecular sieve or composite molecular sieve composed of the above molecular sieves; the organic ligand is organic amine methyl phosphonic acid with different chain lengths, diethylamine, di-n-butylamine and diisooctylamine are used as raw materials to synthesize diethylamine methyl phosphonic acid, dibutylamine methyl phosphonic acid and diisooctylamine methyl phosphonic acid, and the corresponding English names are dibutyl/dimethyl/; (these three acids are referred to in The literature as DEAPA, DBAPA, 2 EAPA.) The generic name of this series of acids is Alkylimidomethylenediphosphonic acid (The Organic ligands diethylamine methylphosphonic acid, dibutylamine methylphosphonic acid or diisooctylamine methylphosphonic acid are prepared here all from The literature MOEDRITZER K, IRANI R. The Direct Synthesis of a-Aminoethylenephosphonic acid acids, Mannich-Type Reactions with Orthophosphonic acids [ J ]. Journal of Organic Chemistry, 1966, 31(5): 1603-1607.)
The silicon-aluminum molecular sieve has a silicon-aluminum ratio of Si: al is stated as 10 to 50, preferably 10 to 35. Titanium-silicon molecular sieve silicon-titanium ratio Si: ti is 20 to 50, preferably 35 to 50.
The pretreated molecular sieve is obtained by acid-base modification, hydrothermal modification and a composite modification method combining the above methods.
The addition amount of the organic ligand and the addition amount of the silicon-aluminum molecular sieve are as follows by phosphorus: the proportion of the aluminum substance is 0.1-3, and the addition of the organic ligand and the titanium silicalite molecular sieve are calculated according to the weight ratio of phosphorus: the proportion value of the titanium substance is 0.1-4 by weight.
The drying temperature is 70-110 ℃, and the drying time is 6-24 h.
The hydrothermal temperature is 30-200 ℃, and the hydrothermal time is 3-48 h.
The reflux temperature is 30-150 ℃, and the reflux time is 0.5-12 h.
The oil-soluble molecular sieve obtained by the modification method is used as an oil product hydrocracking catalyst.
The molecular sieve modification method has the advantages that:
(1) the invention relates to a molecular sieve modification method, which comprises the following raw materials: the molecular sieve comprises a silicon-aluminum molecular sieve, a titanium-silicon molecular sieve and a molecular sieve subjected to acid-base or hydrothermal modification, and the organic ligand is organic amine methyl phosphonic acid with different chain lengths. According to the invention, the molecular sieve is modified by adding the organic ligand, so that the dispersity of the molecular sieve in an oil product can be effectively increased, and the catalytic performance of the molecular sieve in hydrocracking is improved. Thereby effectively solving the problems of poor dispersivity and low cracking caused by easy sedimentation of the traditional inorganic molecular sieve in oil products.
(2) In the organic phosphonic acid ligand, because O in a P-O bond can be combined with cations in the molecular sieve to form an Al-O-P bond or a Ti-O-P bond, a nonpolar organic long chain contained in the ligand can be effectively coated on the surface of the molecular sieve, so that the modified molecular sieve is easy to disperse in oil. The addition of the organic ligand and the addition of the silicon-aluminum molecular sieve defined by the invention are as follows: the proportion of the aluminum substance is 0.1-3, and the addition of the organic ligand and the titanium silicalite molecular sieve are calculated according to the weight ratio of phosphorus: the proportion value of the titanium substance is 0.1-4 by weight. The reason is that the molecular sieve is defined to be suitably acidic and to contain cations sufficient to bind the ligand.
(3) The molecular sieve after the acid-base treatment has a large amount of exposed cations in a non-framework structure exposed due to desiliconization or aluminum, and can be bonded with P to wrap the molecular sieve by the organic long chain.
Drawings
FIG. 1 shows a Fourier infrared spectrum of the modified molecular sieve of the present invention;
FIG. 2 is a diagram of a modified small angle XRD spectrum of the molecular sieve of the present invention;
fig. 3 shows a small-angle XRD spectrum of the modified molecular sieve of the present invention.
Detailed Description
In order to facilitate understanding of the present invention, the technical solutions of the present invention are further described below with reference to the accompanying drawings and the detailed description.
Example 1
The modification scheme described in this example was prepared from the following raw materials:
ZSM-5 type molecular sieve with the silica-alumina ratio of 10;
the organic phosphonic acid ligand DEAPA.
Wherein the total mass of the ZSM-5 type molecular sieve and the organic phosphonic acid ligand DEAPA is 5.335 g.
The organophosphonic acid ligand used in this example has the formula 2R-NCH2PO3H2，Wherein R = C2H5(ii) a P in the raw materials: the Al ratio, expressed as mass, was 0.1.
The molecular sieve modification method in this embodiment is as follows:
(1) dissolving the ZSM-5 molecular sieve in 10 mL of deionized water, fully stirring and heating to 90 ℃;
(2) fully dissolving the ligand DEAPA in 7mL of ethanol;
(3) dropwise adding the solution in the step (2) into the molecular sieve solution in the step (1), keeping stirring and keeping the temperature constant for two hours;
(4) carrying out constant-temperature hydrothermal reaction at 150 ℃ on the product obtained in the step (3), and keeping for 12 h;
(5) carrying out vacuum filtration until the pH of the filtrate is = 7-8, and drying in an electrothermal blowing drying oven at 100 ℃;
(6) and grinding to obtain the modified molecular sieve.
Example 2
The modification scheme described in this example was prepared from the following raw materials:
MCM-41 type molecular sieve with silicon-aluminum ratio of 50
The organophosphonic acid ligand DBAPA.
Wherein the mass of the MCM-41 type molecular sieve and the organic phosphonic acid ligand DBAPA is 15.05 g in total.
Solid sodium hydroxide, 0.2 g.
The organophosphonic acid ligand used in this example has the formula 2R-NCH2PO3H2，Wherein R = C4H9(ii) a P in the raw materials: the Al ratio, expressed as the amount of substance, was 3.
The molecular sieve modification method in this embodiment is as follows:
(1) taking the MCM-41 molecular sieve, adding 50 ml of deionized water, fully stirring and heating to 90 ℃;
(2) adding 0.2 g of NaOH solid into the solution, keeping stirring and keeping the temperature at 90 ℃ for one hour;
(3) carrying out vacuum filtration until the pH of the filtrate is = 7-8, and drying in an electrothermal blowing drying oven at 100 ℃;
(4) grinding, and marking the MCM-41 molecular sieve pretreated by NaOH as a sample G-MCM-NaOH;
(5) dissolving the G-MCM-NaOH molecular sieve in 10 mL of deionized water, fully stirring and heating to 90 ℃;
(6) fully dissolving the ligand DBAPA in 7mL of ethanol;
(7) dropwise adding the solution in the step (6) into the molecular sieve solution in the step (5), and keeping stirring and keeping the temperature constant for two hours;
(8) carrying out constant-temperature hydrothermal reaction at 150 ℃ on the product obtained in the step (7), and keeping for 12 h;
(9) carrying out vacuum filtration until the pH of the filtrate is = 7-8, and drying in an electrothermal blowing drying oven at 100 ℃;
(10) and grinding to obtain the modified molecular sieve.
Example 3
The modification scheme described in this example was prepared from the following raw materials:
Ti-MWW type molecular sieve, the silicon-titanium ratio is 50;
the organic phosphonic acid ligand DEAPA.
Wherein the mass of the Ti-MWW type molecular sieve and the mass of the organic phosphonic acid ligand DEAPA are 18.40 g in total.
The organophosphonic acid ligand used in this example has the formula 2R-NCH2PO3H2，Wherein R = C2H5(ii) a P in the raw materials: the Ti ratio, expressed as the amount of substance, was 4.
The molecular sieve modification method in this embodiment is as follows:
(1) dissolving the Ti-MWW molecular sieve in 10 mL of deionized water, fully stirring and heating to 90 ℃;
(2) fully dissolving the ligand DEAPA in 7mL of ethanol;
(3) dropwise adding the solution in the step (2) into the molecular sieve solution in the step (1), keeping stirring and keeping the temperature constant for two hours;
(4) refluxing the product obtained in the step (3) at a constant temperature of 100 ℃ for 6 hours;
(c) carrying out vacuum filtration until the pH of the filtrate is = 7-8, and drying in an electrothermal blowing drying oven at 100 ℃;
(d) and grinding to obtain the modified molecular sieve.
Example 4
The modification scheme described in this example was prepared from the following raw materials:
USY type molecular sieve with the silicon-aluminum ratio of 25;
organophosphonic acid ligand 2 EAPA;
wherein the mass of the USY type molecular sieve and the mass of the organic phosphonic acid ligand 2EAPA are 5.335g in total.
Citric acid solid, 0.96 g.
The organophosphonic acid ligand used in this example has the formula 2R-NCH2PO3H2，Wherein R = C8H17. P in the raw materials: the Al ratio, expressed as mass, was 0.1.
The molecular sieve modification method in this embodiment is as follows:
(1) adding 50 mL of deionized water into the USY molecular sieve, fully stirring and heating to 90 ℃;
(2) adding 0.96 g of citric acid solid into the solution, keeping stirring and keeping the temperature at 90 ℃ for one hour;
(3) carrying out vacuum filtration until the pH of the filtrate is = 7-8, and drying in an electrothermal blowing drying oven at 100 ℃;
(4) grinding, and marking the USY molecular sieve pretreated by the citric acid as a sample G-USY-N;
(5) dissolving the G-USY-N molecular sieve in 10 mL of deionized water, fully stirring and heating to 90 ℃;
(6) fully dissolving the ligand 2EAPA in 7mL of ethanol;
(7) dropwise adding the solution in the step (6) into the molecular sieve solution in the step (5), and keeping stirring and keeping the temperature constant for two hours;
(8) carrying out constant-temperature hydrothermal reaction at 150 ℃ on the product obtained in the step (7), and keeping for 12 h;
(9) carrying out vacuum filtration until the pH of the filtrate is = 7-8, and drying in an electrothermal blowing drying oven at 100 ℃;
(10) and grinding to obtain the modified molecular sieve.
Examples of the experiments
The modified molecular sieve catalysts prepared according to the four experimental schemes in the working examples are all added with molybdenum isooctanoate for modification experiments, the adding amount of the molybdenum isooctanoate is 600ppm, and the mass ratio of the adding amount of the molybdenum isooctanoate to the adding amount of the molecular sieve is 0.225. The results are described as Experimental example 1, Experimental example 2, Experimental example 3 and Experimental example 4.
Comparative example 1
Only molybdenum isooctanoate was added as catalyst.
Comparative example 2
The experiment was carried out by adding commercial MCM-41 type molecular sieve and molybdenum isooctanoate as comparison.
1. Modified molecular sieve Fourier infrared spectrum
Using MCM-41 type molecular sieve as an example, the modification was performed according to the above examples and numbered as follows:
(1) modifying the MCM-41 type molecular sieve according to the example 2, and recording the modified molecular sieve as G-MCM-NaOH-EAPA;
(2) marking the prepared organic phosphonic acid ligand as EAPA;
(3) commercial MCM-41 type molecular sieves were purchased and designated as M-MCM for comparison.
As can be seen from the Fourier infrared spectrum of FIG. 1, the organic chain is successfully introduced into the molecular sieve, and the modified molecular sieve is easily dispersed in an organic solvent, so that the scheme is proved to be feasible.
2. Modified molecular sieve XRD atlas
Using MCM-41 type molecular sieve as an example, the modification was performed according to the above examples and numbered as follows:
(1) modifying the MCM-41 type molecular sieve according to the example 1, and recording the modified molecular sieve as G-MCM-EAPA, wherein the MCM-41 type molecular sieve pretreated by NaOH is recorded as G-MCM-NaOH;
(2) modifying the MCM-41 type molecular sieve according to the example 2, and recording the modified molecular sieve as G-MCM-NaOH-EAPA;
(3) MCM-41 type molecular sieve was modified as in example 4 and designated G-MCM-N-EAPA, and the citric acid pretreated MCM-41 type molecular sieve was designated G-MCM-N.
The results obtained by performing experiments using a commercial MCM-41 type molecular sieve as a comparison, as shown in FIGS. 2 and 3:
the molecular sieve modification small-angle XRD spectrograms are shown in figures 2 and 3, and it can be seen that the introduction of the organic phosphonic acid ligand has a great influence on the molecular sieve after acid-base modification, which indicates that P can be introduced into the non-framework structure exposed by the modified molecular sieve due to desilication or dealumination, so that the molecular sieve is wrapped by the organic long chain.
3. Activity test of modified molecular sieve applied to suspension bed hydrocracking reaction
The conditions for the activity test of the catalytic addition in this experimental example are as follows. Raw materials: the Clarityl atmospheric residue (KAR) has the reaction pressure of 12Mpa, the reaction temperature of 400 ℃, the content of added molybdenum of 600ppm, the loading of added molecular sieve of 2 wt percent and the reaction time of 2 hours.
Four catalysts prepared in the examples and comparative examples were subjected to activity test, the molybdenum source added was molybdenum isooctanoate, the contents were all 600ppm, and the measurement results were as follows:
as can be seen from the above table, the molecular sieve modified by adding the organophosphonic acid ligand according to the method described herein can be used in the residual oil suspension bed hydrocracking experiment, and compared with the commercial molecular sieve, the liquid yield and the light oil yield of the catalyst can be significantly improved, and the green coke and gas yields can be reduced, and simultaneously the residual oil yield can be reduced. Wherein, the molecular sieve is modified by alkali and then added with organic phosphonic acid ligand for modification, so that the highest liquid yield and the lowest coke rate can be obtained, and the residual oil hydrocracking effect is the best.
4. Dispersion test of modified molecular sieve in oil product
The four catalysts applied to the residual oil suspension bed hydrocracking reaction are taken out after the reaction, cleaned and dried, and subjected to a laser particle size test, wherein the determination result is as follows:
from the above table, it can be seen that, after the organic phosphonic acid ligand is added to the molecular sieve for modification, the average particle size of the molecular sieve catalyst in the oil product is obviously reduced, i.e. the dispersibility of the catalyst in the oil product is improved by the modification method.
Although the present invention has been described in detail with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims.
Claims (10)
1. A method for modifying a molecular sieve, characterized in that the modification step comprises: dissolving an organic ligand in an organic solvent, uniformly mixing the organic ligand with the molecular sieve or the pretreated molecular sieve, regulating the pH value to be acidic or neutral through hydrothermal or reflux treatment, and then filtering and drying to obtain the oil-soluble molecular sieve.
2. The method of claim 1, wherein the molecular sieve is a molecular sieve having a good channel structure and containing metal cations, and comprises a silico-aluminum molecular sieve or a titanium-silicon molecular sieve.
3. The method of modifying a molecular sieve of claim 2, wherein the ratio of the silicoaluminophosphate molecular sieve Si: al is 10-50.
4. The method of modifying a molecular sieve of claim 2, wherein the molar ratio of the titanium silicalite Si: ti is 20-50.
5. The method for modifying a molecular sieve according to claim 1, wherein the pretreated molecular sieve is obtained by acid-base modification, hydrothermal modification or a composite modification method combining the acid-base modification and the hydrothermal modification.
6. The method of claim 1, wherein the organic ligand is diethylamine methylphosphonic acid, dibutylamine methylphosphonic acid, or diisooctylamine methylphosphonic acid.
7. The method for modifying a molecular sieve according to claim 6, wherein the addition amount of the organic ligand and the addition amount of the aluminosilicate molecular sieve are as follows: the proportion of the aluminum substance is 0.1-3, and the addition of the organic ligand and the titanium silicalite molecular sieve are calculated according to the weight ratio of phosphorus: the proportion value of the titanium substance is 0.1-4 by weight.
8. The method for modifying a molecular sieve according to claim 1, wherein the hydrothermal temperature is 30 to 200 ℃ and the hydrothermal time is 3 to 48 hours.
9. The method of claim 1, wherein the reflux temperature is 30-150 ℃ and the reflux time is 0.5-12 h.
10. The modified molecular sieve obtained by the modification method according to any one of claims 1 to 9 is used as a hydrocracking catalyst for oils.
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| 严丽霞等: "多级孔道沸石用于甲醇制丙烯反应研究进展", 《化工进展》 * |
| 霍全等: "HL/HW复合沸石对烃类催化裂化催化剂性能的影响", 《催化学报》 * |
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| CN110980763B (en) | 2022-10-18 |
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