Environment-friendly metal deactivator as well as preparation method and application thereof

Abstract

The invention discloses an environment-friendly metal passivator and a preparation method and application thereof, and the passivator is prepared from the following raw materials in parts by mass: 30-40 parts of deionized water, 30-50 parts of alcohol amine, 20-30 parts of a boron-containing compound, 5-10 parts of a silicon-containing compound, 10-20 parts of a metal passivation accelerant and 5-15 parts of polyhydric alcohol. The metal passivation accelerant is composed of tungsten silicic acid, ammonium molybdate and 0.2-0.5 wt% of xanthan gum water solution, wherein the mass ratio of tungsten silicic acid to ammonium molybdate is (1-3): (1-2): (5-6). The raw materials do not contain toxic and harmful substances, so that in the preparation process, harm to human bodies is reduced, and meanwhile, environmental protection is also facilitated; the preparation process is simple and the raw material cost is low.

Description

Technical Field

[0001] The petrochemical field of the present invention specifically relates to an environmentally friendly metal passivator and a preparation method and application thereof. Background Art

[0002] In the catalytic cracking process, especially the catalytic cracking process using heavy oil as raw material, heavy metals (such as nickel, vanadium, iron, calcium, sodium, etc.) contained in the raw oil will be deposited on the catalyst surface, causing catalyst contamination. As the amount of deposition continues to increase, the activity and selectivity of the catalyst decrease, resulting in an increase in coke and hydrogen, and a decrease in the yield of light oil products. Adding metal passivators to catalytic cracking raw materials is the most economical, simple and effective method to inhibit heavy metal contamination of catalysts.

[0003] At present, most metal passivators contain inorganic or organic compounds of antimony and tin. The antimony and tin in such passivators can form Sn-Ni and Sb-Ni alloys with the harmful metal nickel in the raw oil component to achieve better nickel passivation performance. Since antimony and tin compounds are harmful to the human body and cause environmental pollution, the production of non-toxic passivators is an inevitable choice to adapt to the development of clean production while effectively suppressing metal pollution.

[0004] CN 107971042 A discloses a method for preparing a catalytic cracking metal passivator, which comprises: a. mixing antimony trioxide, hydroxycarboxylic acid, boron-containing compound, rare earth salt, pH regulator and water, reacting for 30-60 minutes at a temperature of 20-90°C to obtain a first product; b. mixing an oxidant with the first product obtained in step a, reacting in a closed container for 1-2 hours at a temperature of 100-150°C to obtain a catalytic cracking metal passivator. The method for preparing a catalytic cracking metal passivator provided by the invention has the advantages of simple preparation process, short reaction time, low cost, reduced energy consumption, and significant economic benefits. The catalytic cracking metal passivator prepared by the method exhibits good passivation of nickel and vanadium when used in a catalytic cracking reaction, can significantly increase the light oil yield, and reduce the proportion of coke and dry gas in the product. Although boron-containing compounds are added to the raw materials of the metal passivator of the invention to replace part of the antimony oxide and make the product environmentally friendly, the boron-containing compounds cannot form an effective passivation effect in the metal system, and the antimony oxide component still plays the main role. The preparation process will cause certain pollution to the environment and increase the harm to the operators.

[0005] CN100338183C discloses a catalytic cracking liquid auxiliary agent, preparation and application thereof. The liquid auxiliary agent is composed of one or more metals selected from rare earth elements, Zn, Ti, Mg, Sn, Ba, Zn and one or more organic acids selected from organic carboxylic acids, hydroxy acids, carbonyl acids, benzenesulfonic acids and organic phosphonic acids. The metal element content accounts for 1-25% by weight of the liquid auxiliary agent, and the carbon chain length of the organic acid is C 1 -C 26 The additive can reduce the olefin content by 5-7 percentage points and increase the light oil yield by 5-11 percentage points while keeping the octane number of the product gasoline basically unchanged. The raw materials of the invention do not contain toxic substances and are environmentally friendly, but the raw materials of the invention contain a large amount of rare earth metals, which increases the production cost. At the same time, too much heavy metals in the raw materials will also cause certain pollution to the catalyst.

[0006] CN102974398A discloses a method for preparing an environmentally friendly multifunctional metal passivator, wherein the passivator is prepared from raw materials: water, boric acid, metal ion passivator, glycerol, and magnesium acetate. The environmentally friendly multifunctional metal passivator prepared by the invention changes the use of antimony, tin, and rare earth metals in the prior art, avoids heavy metal pollution, reduces the use cost without affecting the passivation effect, and saves mineral resources. The disadvantage of the invention is that Mg in the raw material component is an alkaline earth metal, has strong mobility, and is easy to enter the molecular sieve pores. Excessive use will reduce the thermal stability of the molecular sieve, destroy the molecular sieve structure, and shorten the life of the catalyst.

[0007] CN111054449A discloses an environmentally friendly multi-metal passivator, comprising the following components by weight: 50-60 parts of boric acid, 20-30 parts of glycerol, 10-15 parts of calcium stearate, 10-15 parts of sodium carbonate, 5-10 parts of sodium hydroxide and 30-40 parts of deionized water. All raw material components of the invention are inorganic compounds, which have a higher melting point than organic hydrocarbons and are more convenient and safer to store; the invention mainly uses boron compounds and calcium compounds as raw materials to synthesize inhibitors for multiple metals such as nickel, alum and aluminum; the raw materials of the invention do not contain any harmful substances, which is beneficial to environmental protection, reduces harm to operators, and has no adverse effects on downstream processing and product quality; compared with traditional rare earth inhibitors, the invention saves the country's rare earth resources and reduces the production costs of enterprises. The disadvantage of this invention is that the passivation component contains polluting metals Na and Ca, which will be enriched on the catalyst surface while passivating the harmful metals. When accumulated to a certain amount, it will cause catalyst contamination due to excessive concentration of the passivation component, thereby affecting the physical properties and catalyst properties of the catalyst.

[0008] CN200510030083.X discloses a catalytic cracking metal passivator and a preparation method thereof, providing compounds containing boron and boron and phosphorus as catalytic cracking metal passivators. The invention does not use toxic components such as Sb and has a significant passivation effect on nickel on the catalyst.

[0009] The above technologies have two main defects:

[0010] (1) The components contain toxic antimony, which is harmful to the human body and also causes environmental pollution.

[0011] (2) The components do not contain toxic substances such as S, P, Sb, Sn, etc.:

[0012] The raw material components contain alkaline earth metal Mg, which has strong mobility and can easily enter the pores of the molecular sieve. Excessive use will reduce the thermal stability of the molecular sieve, destroy the molecular sieve structure, and shorten the life of the catalyst.

[0013] The raw material components themselves contain polluting metals Na and Ca, which will be enriched on the catalyst surface while passivating harmful metals. When accumulated to a certain amount, it will cause catalyst contamination due to excessive concentration of passivating components, thereby affecting the activity of the catalyst.

[0014] The raw material components contain only non-metallic components, resulting in low passivation efficiency of the passivator. Summary of the invention

[0015] The purpose of the present invention is to provide an environmentally friendly metal passivator, the raw material components of the passivator do not contain toxic components, while taking into account the non-toxic and harmless, and ensuring that the passivator does not cause pollution to the catalyst itself during long-term use, and has high passivation efficiency.

[0016] Another object of the present invention is to provide a method for preparing an environmentally friendly metal passivator.

[0017] Another object of the present invention is to provide an application of an environmentally friendly metal passivator.

[0018] To achieve the above-mentioned purpose, the present invention provides an environmentally friendly metal passivator. The raw materials for preparation include, by weight, 30-40 parts of deionized water, 30-50 parts of alcohol amine, 20-30 parts of boron-containing compounds, 5-10 parts of silicon-containing compounds, 10-20 parts of metal passivation promoters and 5-15 parts of polyols; the metal passivation promoter is composed of tungstosilicic acid, ammonium molybdate and 0.2-0.5wt% xanthan gum aqueous solution in a mass ratio of 1-3:1-2:5-6.

[0019] In the environmentally friendly metal passivator of the present invention, the alcohol amine is one or more of ethanolamine, propanolamine, butanolamine, diethanolamine and triethanolamine.

[0020] The environmentally friendly metal passivator of the present invention, the boron-containing compound is boric acid and / or boron trioxide.

[0021] The environmentally friendly metal passivator of the present invention, the silicon-containing compound is silicic acid.

[0022] The environmentally friendly metal passivator of the present invention, the polyol is one or more of ethylene glycol, glycerol, 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol and neopentyl glycol.

[0023] The environmentally friendly metal passivator of the present invention comprises, by weight, 30-40 parts of deionized water, 40-50 parts of diethanolamine and / or triethanolamine, 25-30 parts of boric acid and / or boron trioxide, 5-10 parts of silicic acid, 15-20 parts of metal passivation accelerator and 10-15 parts of propylene glycol.

[0024] The environmentally friendly metal passivator of the present invention is prepared by mixing xanthan gum and deionized water, heating to 70-90°C, stirring to obtain a xanthan gum aqueous solution, adjusting the temperature to 50-70°C, adding ammonium molybdate and tungstosilicic acid, and stirring to obtain a metal passivation accelerator.

[0025] To achieve the above purpose, the present invention also provides a method for preparing an environmentally friendly metal passivator. Deionized water, alcohol amine, boron-containing compound, silicon-containing compound and polyol are added to a reaction kettle in sequence, the temperature is controlled at 50-80°C and heated for 1-2h, a metal passivation promoter is added and the temperature is raised to 80°C, the heating is continued to boil and reflux for 20min-1h, and the metal passivator is obtained by cooling.

[0026] To achieve the above object, the present invention also provides an application of an environmentally friendly metal passivator in catalyst cracking.

[0027] Beneficial effects of the present invention:

[0028] (1) The nickel passivation component in the raw material of the present invention does not contain Na, Mg, and Ca metal components, which can prevent the metal components of the passivator from causing secondary pollution to the catalyst during long-term use, thereby affecting the activity and life of the catalyst.

[0029] (2) The raw materials of the present invention do not contain any toxic or harmful substances, which reduces the harm to the human body during the preparation process and is also beneficial to environmental protection.

[0030] (3) The preparation process of the present invention is simple and the raw material cost is low.

[0031] (4) The boron oxide and silicon oxide generated by the boron-containing compound and the silicon-containing compound at the regeneration temperature react with NiO to generate Ni 2 B 2O 5 and Ni 2 SiO 4 , thereby reducing the reduction degree of high-valent nickel under the reaction conditions in the reactor, inhibiting the dehydrogenation activity of low-valent nickel, and achieving the purpose of passivating nickel; the metal passivation promoter component can not only provide catalytic reaction active centers, but also accelerate the reaction process of removing nickel metal components from organic macromolecules, thereby improving the efficiency of the nickel passivation reaction. DETAILED DESCRIPTION

[0032] The present invention is described in detail below by way of examples. It is necessary to point out that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Those skilled in the art in this field can make some non-essential improvements and adjustments to the present invention based on the above content of the present invention.

[0033] The drugs used in the examples are all chemically pure reagents.

[0034] Embodiment 1:

[0035] The passivating agent is prepared according to the method provided by the invention.

[0036] Mix xanthan gum and deionized water, heat to 70°C, stir to obtain a 0.3% xanthan gum aqueous solution, add ammonium molybdate and tungstosilicic acid (the mass ratio of tungstosilicic acid: ammonium molybdate: 0.3% xanthan gum aqueous solution is 3:2:6), stir for 1 hour, and obtain a metal passivator.

[0037] 38 parts of deionized water, 40 parts of triethanolamine, 30 parts of boric acid, 10 parts of silicic acid and 12 parts of propylene glycol were added into a reactor with reflux and condensation in sequence, heated and heated, the temperature was controlled at 60°C for 1 hour, 20 parts of metal passivation promoter were added, the temperature was raised to 80°C, and the heating and boiling reflux were continued for 30 minutes, and the metal passivator was obtained by cooling to room temperature.

[0038] Embodiment 2:

[0039] The passivating agent is prepared according to the method provided by the invention.

[0040] Mix xanthan gum and deionized water, heat to 90°C, and stir to obtain a 0.2% xanthan gum aqueous solution. After adjusting the temperature of the xanthan gum aqueous solution to 70°C, add ammonium molybdate and tungstosilicic acid (the mass ratio of tungstosilicic acid: ammonium molybdate: 0.2% xanthan gum aqueous solution is 2:1:5), stir for 1 hour, and add to the xanthan gum aqueous solution in a mass ratio to obtain a metal passivator.

[0041] 31 parts of deionized water, 45 parts of diethanolamine, 25 parts of boron trioxide, 8 parts of silicic acid and 11 parts of ethylene glycol were added in sequence into a reactor with reflux and condensation, heated and heated at 65°C for 1.5 hours, 17 parts of metal passivation promoter were added, the temperature was raised to 80°C, and the heating was continued to boil and reflux for 20 minutes, and the metal passivation agent was obtained by cooling to room temperature.

[0042] Embodiment 3:

[0043] The passivating agent is prepared according to the method provided by the invention.

[0044] Mix xanthan gum and deionized water, heat to 90°C, and stir to obtain a 0.5% xanthan gum aqueous solution. After adjusting the temperature of the xanthan gum aqueous solution to 50°C, add ammonium molybdate and tungstosilicic acid (the mass ratio of tungstosilicic acid: ammonium molybdate: 0.5% xanthan gum aqueous solution is 2:1:6), stir for 1 hour, and add to the xanthan gum aqueous solution in a mass ratio to obtain a metal passivator.

[0045] 30 parts of deionized water, 35 parts of butanolamine, 20 parts of boric acid, 7 parts of silicic acid, and 15 parts of 1,2-propylene glycol are added in sequence into a reactor with reflux and condensation, and the temperature is heated and controlled at 50°C for 2 hours. 15 parts of a metal passivation promoter are added, the temperature is raised to 80°C, and the heating is continued to boil and reflux for 40 minutes. The metal passivator is obtained by cooling to room temperature.

[0046] Embodiment 4:

[0047] The passivating agent is prepared according to the method provided by the invention.

[0048] Mix xanthan gum and deionized water, heat to 70°C, and stir to obtain a 0.4% xanthan gum aqueous solution. After adjusting the temperature of the xanthan gum aqueous solution to 50°C, add ammonium molybdate and tungstosilicic acid (the mass ratio of tungstosilicic acid: ammonium molybdate: 0.4% xanthan gum aqueous solution is 3:1:6), stir for 1 hour, and add to the xanthan gum aqueous solution in a mass ratio to obtain a metal passivator.

[0049] 35 parts of deionized water, 30 parts of propanolamine, 30 parts of boron trioxide, 6 parts of silicic acid and 8 parts of neopentyl glycol were added in sequence into a reactor with reflux and condensation, heated and heated, the temperature was controlled at 80°C for 1.5 hours, 20 parts of metal passivation promoter were added, and the heating was continued to boil and reflux for 50 minutes, and cooled to room temperature to obtain a metal passivator.

[0050] Embodiment 5:

[0051] The passivating agent is prepared according to the method provided by the invention.

[0052] Mix xanthan gum and deionized water, heat to 70°C, and stir to obtain a 0.1% xanthan gum aqueous solution. After adjusting the temperature of the xanthan gum aqueous solution to 50°C, add ammonium molybdate and tungstosilicic acid (the mass ratio of tungstosilicic acid: ammonium molybdate: 0.1% xanthan gum aqueous solution is 1:2:5), stir for 1h, and add to the xanthan gum aqueous solution in a mass ratio to obtain a metal passivator.

[0053] 32 parts of deionized water, 50 parts of ethanolamine, 25 parts of boric acid, 5 parts of silicic acid and 5 parts of 1,6-hexanediol were added in sequence into a reactor with reflux and condensation, heated and heated at 65°C for 1.5 hours, 10 parts of metal passivation promoter were added, the temperature was raised to 80°C, and the heating was continued to boil and reflux for 1 hour, and cooled to room temperature to obtain a metal passivator.

[0054] Comparative Example 1:

[0055] An environmentally friendly metal passivator is prepared according to the prior art.

[0056] Add 64 ml of 6 mol / L dilute nitric acid and 12 g of magnesium carbonate to a three-necked flask for magnesium salt ionization reaction. After the magnesium salt is completely dissolved, add 30 g of triethanolamine and react with magnesium ions at 55°C for 3 hours. After the reaction is completed, add DMF with a molar ratio of 1:1 to the magnesium complex and react for further 2 hours at 80°C to obtain a transparent water-soluble environmentally friendly passivating agent.

[0057] Comparative Example 2:

[0058] The commercially available antimony-based passivator (JCM-9E1) was used, and the density (20°C) was 1.45 g / cm 3 , kinematic viscosity (20℃) is 4.2mm 2 / s, antimony content: 25.6%.

[0059] Comparative Example 3

[0060] The passivating agent is prepared according to the method provided by the invention.

[0061] 38 parts of deionized water, 40 parts of triethanolamine, 30 parts of boric acid, 10 parts of silicic acid and 12 parts of propylene glycol were added into a reactor with reflux and condensation in sequence, heated and heated at 60°C for 1 hour, 20 parts of tungstosilicic acid were added and heated to 80°C, and the heating and boiling reflux were continued for 30 minutes, and the metal passivator was obtained by cooling to room temperature.

[0062] Test Example:

[0063] The metal passivator prepared in Example 1-5 was diluted with deionized water, and then impregnated on a Lanzhou Petrochemical balancer with a Ni content of 2700 ppm, dried at 140° C., and then baked at 650° C. for 5 h to prepare a test balancer SY1-5.

[0064] Test comparison ratio:

[0065] The metal passivator obtained in Comparative Examples 1-3 was diluted with deionized water and impregnated on a Lanzhou Petrochemical balancer with a Ni content of 2700ppm. After drying at 140°C, it was baked at 650°C for 5h to prepare a comparative balancer DB-1 with a magnesium content of 5000ppm, a comparative balancer DB-2 with an antimony content of 3000ppm, a comparative balancer DB-3, and a blank balancer control group DB-0 without passivator impregnation.

[0066] Performance Testing

[0067] Performance tests were carried out on a fluid catalytic cracking riser unit designed and developed by Luoyang Petrochemical Engineering Company.

[0068] Using Lanzhou Petrochemical catalyst as raw material, five kinds of balance agents were evaluated in a fluidized catalytic cracking reactor. The evaluation conditions were: catalyst loading of 4kg, reaction temperature of 543℃, reaction pressure of 30kPa, catalyst-oil ratio of 6.94, reaction time of 2s, and oil feed rate of 1.5kg / h. The raw oil parameters are shown in Table 1, the properties of Lanzhou Petrochemical balance agents are shown in Table 2, and the experimental results are listed in Table 3.

[0069] Table 1 Raw oil properties

[0070]

[0071]

[0072] Table 2 Main properties of Lanzhou Petrochemical equilibrium catalyst

[0073]

[0074] Table 3 Product distribution of catalytic cracking with different balance agents

[0075]

[0076] It can be shown from Table 3 that the catalytic cracking metal passivator prepared by the present invention has an obvious passivation effect on the harmful metal nickel on the catalytic cracking catalyst. Under the same conditions, the light oil yield of the balance agent treated with the passivator of the present invention is increased by 4.37-5.88 percentage points, the dry gas is reduced by 0.74-0.91 percentage points, and the coke is reduced by 0.94-1.19 percentage points compared with the catalyst not treated with the passivator; it can also be seen from Table 3 that the light oil yield of the balance agent SY-1 treated with the passivator of the present invention is increased by 1.62 percentage points, the dry gas is reduced by 0.22 percentage points, and the coke is reduced by 0.43 percentage points compared with the catalyst treated with the antimony series passivator, and the effect is better than the antimony series passivator. Compared with DB-3 (only tungstosilicic acid is added as the metal passivation promoter), the light oil yield of the balance agent SY-1 treated with the passivator of the present invention increases by 1.76 percentage points, the dry gas yield decreases by 0.5 percentage points, and the coke yield decreases by 0.77 percentage points; compared with the existing environmentally friendly magnesium-based passivator, the light oil yield of the balance agent SY-1 treated with the passivator of the present invention increases by 3.83 percentage points, the dry gas yield decreases by 0.61 percentage points, and the coke yield decreases by 0.76 percentage points, which is better than the environmentally friendly magnesium-based passivator. In addition, the metal passivator of the present invention has the characteristics of being non-toxic and environmentally friendly, and therefore has a good utilization prospect.

[0077] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, technicians familiar with the field may make various corresponding changes and deformations based on the present invention, but these corresponding changes and deformations should all fall within the scope of protection of the claims of the present invention.

Claims

1. An environmentally friendly metal passivator, characterized in that: The raw materials include 30-40 parts of deionized water, 30-50 parts of alcohol amine, 20-30 parts of boron-containing compounds, 5-10 parts of silicon-containing compounds, 10-20 parts of metal passivation promoters and 5-15 parts of polyols in parts by mass; the metal passivation promoter is composed of tungstosilicic acid, ammonium molybdate and 0.2-0.5wt% xanthan gum aqueous solution in a mass ratio of 1-3:1-2:5-6.

2. The environmentally friendly metal passivator according to claim 1, characterized in that: The alcoholamine is one or more of ethanolamine, propanolamine, butanolamine, diethanolamine and triethanolamine.

3. The environmentally friendly metal passivator according to claim 1, characterized in that: The boron-containing compound is boric acid and / or boron trioxide.

4. The environmentally friendly metal passivator according to claim 1, characterized in that: The silicon-containing compound is silicic acid.

5. The environmentally friendly metal passivator according to claim 1, characterized in that: The polyol is one or more of ethylene glycol, glycerol, 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol and neopentyl glycol.

6. The environmentally friendly metal passivator according to claim 1, characterized in that: The raw materials include, by weight, 30-40 parts of deionized water, 40-50 parts of diethanolamine and / or triethanolamine, 25-30 parts of boric acid and / or boron trioxide, 5-10 parts of silicic acid, 15-20 parts of metal passivation promoter and 10-15 parts of propylene glycol.

7. The environmentally friendly metal passivator according to claim 1, characterized in that: The preparation method of the metal passivation accelerator is as follows: xanthan gum and deionized water are mixed, the temperature is raised to 70-90° C., and agitation is performed to obtain a xanthan gum aqueous solution, and the temperature is adjusted to 50-70° C., and then ammonium molybdate and tungstosilicic acid are added, and agitation is performed to obtain the metal passivation accelerator.

8. The method for preparing the environmentally friendly metal passivator according to any one of claims 1 to 7, characterized in that: Deionized water, alcohol amine, boron-containing compound, silicon-containing compound and polyol are added to the reaction kettle in sequence, the temperature is controlled at 50-80°C and heated for 1-2 hours, after adding the metal passivation accelerator, the heating is continued to boil and reflux for 20 minutes to 1 hour, and the metal passivator is obtained by cooling.

9. Use of the environmentally friendly metal passivator according to any one of claims 1 to 7 or the environmentally friendly metal passivator prepared by the preparation method according to claim 8 in catalyst cracking.

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