阅读说明：本技术 一种S-Zorb工艺辛烷值助剂及其制备方法 (S-Zorb process octane number auxiliary agent and preparation method thereof ) 是由 于向真 于 2021-02-10 设计创作，主要内容包括：本发明公开了一种S-Zorb工艺提高汽油辛烷值的助剂及其制备方法,所述助剂以金属氧化物改性的ZSM-5、beta、丝光沸石或纯硅分子筛为活性组元,助剂含有10%～70%的改性分子筛、10%～50%的黏土、0～35%的拟薄水铝石、3%～30%的粘结剂,助剂平均粒度在65～130微米。本发明助剂与S-Zorb吸附剂一起使用,通过异构化、芳构化来保持或提高汽油的辛烷值,可以提高汽油的辛烷值(RON)0.5个点以上。(The invention discloses an auxiliary agent for improving gasoline octane number by an S-Zorb process and a preparation method thereof, wherein the auxiliary agent takes metal oxide modified ZSM-5, beta, mordenite or a pure silicon molecular sieve as an active component, the auxiliary agent contains 10-70% of modified molecular sieve, 10-50% of clay, 0-35% of pseudo-boehmite and 3-30% of binder, and the average particle size of the auxiliary agent is 65-130 micrometers. The auxiliary agent is used together with the S-Zorb adsorbent, maintains or improves the octane number of the gasoline through isomerization and aromatization, and can improve the octane number (RON) of the gasoline by more than 0.5 point.)

1. The octane number auxiliary agent for the S-Zorb process is characterized by comprising 10-70% of modified molecular sieve, 10-50% of clay, 0-35% of pseudo-boehmite and 3-30% of binder by weight of dry basis, wherein the average particle size of the auxiliary agent is 65-130 microns.

2. An S-Zorb process octane booster of claim 1 wherein the modified molecular sieve is at least one of ZSM-5 in the hydrogen form modified with a metal oxide, beta molecular sieve, mordenite, or pure silicalite.

3. An octane number enhancer according to claim 2 wherein the metal oxide is at least one metal selected from the group consisting of cobalt, nickel, molybdenum, tungsten, platinum, palladium, chromium, iron and zinc.

4. An S-Zorb process octane aid of claim 1 wherein the clay is at least one member selected from the group consisting of kaolin, halloysite, bentonite, rectorite, sepiolite, attapulgite, and diatomaceous earth.

5. An octane auxiliary of S-Zorb process as claimed in claim 1, wherein the binder is at least one of silica sol, alumina sol, aluminophosphate gel, acidified pseudoboehmite, or silica alumina gel.

6. The method for preparing the octane number auxiliary of the S-Zorb process according to any one of claims 1 to 5, comprising the steps of:

(1) saturated impregnation of the molecular sieve with an aqueous solution containing a metal salt, metal oxide: the molecular sieve is = 0-0.12: 1, and the modified molecular sieve is obtained;

(2) mixing clay, pseudo-boehmite and a binder together, and adding a certain amount of water to pulp, wherein the solid content is controlled to be 20-50%;

(3) and (2) adding the modified molecular sieve prepared in the step (1), uniformly mixing, and then carrying out spray drying and roasting to obtain the auxiliary agent.

Technical Field

The invention belongs to the field of petrochemical catalysts, and particularly relates to an auxiliary agent for improving octane number in a gasoline selective hydrodesulfurization adsorption process S-Zorb and a preparation method thereof.

Background

When the sulfides in the gasoline are combusted, the sulfides are converted into the sulfur oxides to be released into the air, acid mist or acid rain and the like can be formed to pollute the environment and harm the human health, national V standard is initially implemented in 2012, and the sulfur content in the gasoline is regulated to be reduced to below 10 mu g/g.

Among all gasoline desulfurization processes, the S-Zorb selective hydrogenation adsorption desulfurization process is a widely-applied process in the desulfurization technology, has the advantages of high desulfurization rate, low product sulfur content, low hydrogen consumption, small octane number loss and the like, and has obvious technical advantages in the production of gasoline with ultra-low sulfur. The adsorbent for reactive adsorption desulfurization mainly comprises an active component and a carrier, wherein the active component comprises active metal and zinc oxide, the active metal is an active center for adsorbing sulfide, the zinc oxide is a sulfur-containing component, the carrier generally comprises metal oxide and non-metal oxide, and the commonly used active metal is simple substance Ni and is used as the active center for reactive adsorption.

In the S-Zorb selective hydrogenation adsorption desulfurization process, partial olefin is subjected to hydrogenation saturation while the sulfur is removed through hydrogenation, and the olefin is a high-octane value component, so that the octane value of the gasoline is reduced to a certain extent, and the loss of the octane value is generally between 0.3 and 1.0.

How to be a new problem in the S-Zorb process is that it is necessary to provide a new auxiliary agent and a preparation method thereof for the S-Zorb process, which can maintain or improve the octane number of gasoline.

Disclosure of Invention

The invention aims to overcome the defects of the existing S-Zorb process, make up the octane number loss of gasoline treated in the S-Zorb process, and invent an auxiliary agent to maintain or improve the octane number of the gasoline.

The invention provides an S-Zorb process octane number auxiliary agent which is characterized by comprising 10-70% of modified molecular sieve, 10-50% of clay, 0-35% of pseudo-boehmite and 3-30% of binder by weight of a dry basis, wherein the average particle size of the auxiliary agent is 65-130 microns.

The invention also provides a preparation method of the octane number auxiliary agent for the S-Zorb process, which is characterized by comprising the following steps:

(1) and saturating and impregnating the molecular sieve with an aqueous solution containing metal salt, wherein the weight ratio of metal oxide: the molecular sieve is = 0-0.12: 1, and the modified molecular sieve is obtained;

(2) mixing clay, pseudo-boehmite, a binder and the like, and adding a certain amount of water to perform slurrying, wherein the solid content is controlled to be 20-50%;

(3) and (3) adding the modified molecular sieve prepared in the step (1), uniformly mixing, and then carrying out spray drying and roasting to obtain the auxiliary agent.

The molecular sieve is at least one of hydrogen type ZSM-5, beta molecular sieve, mordenite or pure silicon molecular sieve.

The aqueous solution containing metal salt is an aqueous solution containing at least one metal selected from cobalt, nickel, molybdenum, tungsten, platinum, palladium, chromium, iron and zinc.

The clay is at least one of kaolin, halloysite, bentonite, rectorite, sepiolite, attapulgite and diatomite.

The binder is at least one of silica sol, alumina sol, phosphor-alumina gel, acidified pseudo-boehmite or silica-alumina gel.

The invention adopts modified ZSM-5, beta, mordenite or pure silicon molecular sieve, and maintains or improves the octane number of the gasoline through isomerization and aromatization.

The auxiliary agent of the invention is directly added into the existing S-Zorb process reaction system and is used together with the S-Zorb adsorbent, and the octane number (RON) of the gasoline can be improved by more than 0.5 point.

Detailed Description

The following detailed description of specific embodiments of the invention is provided by way of example, and it is to be understood that the specific embodiments described herein are merely illustrative and explanatory of the disclosure and are not restrictive thereof.

The analysis method referred to in the present invention is compiled by reference to "analytical methods in petrochemical industry", Yangcui et al, 1990 edition.

Some of the raw materials used in the examples had the following properties:

the pseudoboehmite is an industrial product produced by Shandong aluminum industry company, Al₂O₃The weight content is 68.5 percent;

the aluminum sol is an industrial product, Al, produced by Sichuan Runhe & catalytic materials, Inc₂O₅The content was 21.5 wt%;

the silica sol is an industrial product, SiO, produced by Qingdao Jieyida corporation₂The content was 30.2% by weight, Na₂The content of O is 0.2 percent;

the kaolin is special kaolin No. 1 produced by Suzhou kaolin company, and the dry content is 70.0 weight percent.

Hydrochloric acid concentration of 36 wt%, technical grade;

the ZSM-5 molecular sieve is an industrial product of a Nankai catalyst factory, and the silica-alumina ratio is 60-880;

the Beta molecular sieve is an industrial product of Olympic catalytic material Co., Ltd, and the silica-alumina ratio is 30-650;

the mordenite is an industrial product of Mian Yuan Source catalyst Limited in Tian Chang city, and the silicon-aluminum ratio is 30-720;

evaluation of the auxiliaries, based on the industrial S-Zorb adsorbent FCAS-R09, the starting material was a catalytic gasoline, the composition and properties of which are as follows (Table 1)

TABLE 1 catalytic gasoline Properties (feedstocks)

Analysis item	Numerical value	Remarks for note
			Density (Kg/m3) at 20 DEG C	723.5
The process comprises the following steps: c
			IBP	36.5
10%	52.0
			50%	98.8
90%	171.6
			EP	202.3
S content (μ g/g)	265
			N-alkanes% m	8.23
Isoparaffin% m	31.65
			Olefin% m	28.67
Cycloalkane% m	8.76
			Aromatic hydrocarbon% m	22.69
Octane Number (RON)	89.2

The evaluation device is a small fixed bed reaction device, the loading of the adsorbent and the auxiliary agent is 2g, the continuous feeding is carried out, and the evaluation conditions are as follows: the reaction temperature is 420 ℃, the reaction pressure is 2.5Mpa, and the weight space velocity is 4h^-1The volume ratio of hydrogen to oil was 0.3. PONA analysis was performed by simulated distillation and octane number (RON) analysis of gasoline was performed on a gas chromatograph ((Agilent 6890) and Flame Ion Detector (FID) equipped with a capillary column (PONA,50mx0.2mm, idx0.5um).

Example 1

Adding 366g of ZSM-5 molecular sieve (the silica-alumina ratio is 135, the Na2O is less than 0.01%, the ignition loss is 18%) into 300g of deionized water solution in which 29.2g of nickel nitrate is dissolved, mixing and stirring for 30 minutes to prepare modified molecular sieve slurry for later use;

155g of pseudo-boehmite (burned off by 31.5%) is taken, 550g of deionized water is added for slurrying, then 35g of phosphoric acid with the concentration of 75% and 210g of nitric acid with the concentration of 56% are added, stirring and slow heating are carried out to 90 ℃, 342g of kaolin (the dry basis content is 70%) is added after the pseudo-boehmite is completely dissolved into transparent colloid, and kaolin slurry is prepared after full stirring for 2 hours.

Adding the molecular sieve slurry into the kaolin slurry, fully stirring for 1h, then spray-drying, and roasting at 500 ℃ for 2h to obtain an auxiliary agent sample cat-A. The auxiliary agent contains 46 percent of molecular sieve, 35.5 percent of kaolin and 18.5 percent of phosphor-aluminum glue by weight of dry basis, and the average particle size of the auxiliary agent is 85.6 mu m.

Example 2

Taking 378g of ZSM-5 molecular sieve (the silica-alumina ratio is 245, the Na2O is less than 0.01 percent, and the ignition loss is 20.5 percent), adding the molecular sieve into 300g of deionized water solution in which 118g of nickel nitrate is dissolved, mixing and stirring the mixture for 30 minutes to prepare modified molecular sieve slurry for later use;

365g of kaolin is added into 550g of deionized water, 368g of silica sol is added, and the mixture is fully stirred and pulped for 2 hours to prepare kaolin slurry.

Adding the molecular sieve slurry into the kaolin slurry, fully stirring for 1h, then spray-drying, and roasting at 500 ℃ for 2h to obtain an auxiliary agent sample cat-B. The auxiliary agent contains 46.5 percent of molecular sieve, 38 percent of kaolin and 15.5 percent of silica sol by weight of dry basis, and the average particle size of the auxiliary agent is 91.2 mu m.

Example 3

419.3g of ZSM-5 molecular sieve (the silica-alumina ratio is 245, the Na2O is less than 0.01 percent, the ignition loss is 20.5 percent), 214g of Beta molecular sieve (the silica-alumina ratio is 45, the Na2O is less than 0.01 percent, the ignition loss is 22 percent) are taken and added into 600g of deionized water solution in which 58.4g of nickel nitrate is dissolved, and the mixture is mixed and stirred for 30 minutes to prepare modified molecular sieve slurry for later use;

267.5g of pseudo-boehmite (burned off by 31.5%) is taken, 1000g of deionized water is added for slurrying, 62g of phosphoric acid with the concentration of 75% is added, 365g of nitric acid with the concentration of 56% is added, stirring is carried out, the temperature is slowly raised to 90 ℃, when the pseudo-boehmite is completely dissolved into transparent colloid, 561g of kaolin (the dry basis content is 70%) is added, and the mixture is fully stirred for 2 hours to prepare kaolin slurry.

Adding the molecular sieve slurry into the kaolin slurry, fully stirring for 1h, then spray-drying, and roasting at 500 ℃ for 2h to obtain an auxiliary agent sample cat-C. The auxiliary agent contains 46.3 percent of molecular sieve, 35.2 percent of kaolin and 18.5 percent of phosphor-aluminum glue by weight of dry basis, and the average particle size of the auxiliary agent is 88.1 mu m.

Example 4

Taking 636g of mordenite (the silica-alumina ratio is 35, the Na2O is less than 0.01 percent, the ignition loss is 21.5 percent), adding the mordenite into 600g of deionized water solution in which 93.5g of nickel nitrate is dissolved, mixing and stirring for 30 minutes to prepare modified molecular sieve slurry for later use;

720g of kaolin is added into 950g of deionized water, 813g of silica sol is added, and the mixture is fully stirred and pulped for 3 hours to prepare kaolin slurry.

Adding the molecular sieve slurry into the kaolin slurry, fully stirring for 1h, then spray-drying, and roasting at 500 ℃ for 2h to obtain an auxiliary agent sample cat-D. The auxiliary agent contains 41.6 percent of modified molecular sieve, 40 percent of kaolin and 18.4 percent of silica sol by weight of dry basis, and the average particle size of the auxiliary agent is 89.3 mu m.

Example 5

Adding 610g of ZSM-5 molecular sieve (the silica-alumina ratio is 135, the Na2O is less than 0.01%, the ignition loss is 18%) into 650g of deionized water solution in which 48.7g of nickel nitrate and 9.2g of ammonium molybdate are dissolved, and mixing and stirring for 30 minutes to prepare modified molecular sieve slurry for later use;

taking 262g of pseudo-boehmite (burned off by 31.5 percent), adding 650g of deionized water for slurrying, then adding 60g of phosphoric acid with the concentration of 75 percent and 370g of nitric acid with the concentration of 56 percent, stirring and slowly heating to 90 ℃ until the pseudo-boehmite is completely dissolved into transparent colloid, then adding 408g of kaolin (with the dry basis content of 70 percent), and fully stirring for 2 hours to prepare kaolin slurry.

Adding the molecular sieve slurry into the kaolin slurry, fully stirring for 1h, then spray-drying, and roasting at 500 ℃ for 2h to obtain an auxiliary agent sample cat-E. The auxiliary agent contains 51 percent of modified molecular sieve, 28 percent of kaolin and 21 percent of phosphor-aluminum gel by weight of dry basis, and the average particle size of the auxiliary agent is 78.6 mu m.

Example 6

Adding 311g of ZSM-5 molecular sieve (the silica-alumina ratio is 225, the Na2O is less than 0.01%, and the ignition loss is 3.5%) into 300g of deionized water solution in which 58.4g of nickel nitrate and 21.9g of zinc nitrate are dissolved, and mixing and stirring for 30 minutes to prepare modified molecular sieve slurry for later use;

adding 289g of silica sol into 550g of deionized water, adding 285g of kaolin, adding 116g of pseudo-boehmite, and fully stirring and slurrying for 4 hours to prepare kaolin slurry.

Adding the molecular sieve slurry into the kaolin slurry, fully stirring for 1h, then spray-drying, and roasting at 500 ℃ for 2h to obtain an auxiliary agent sample cat-F. The auxiliary agent contains 46.7 percent of modified molecular sieve, 29 percent of kaolin, 11.6 percent of pseudo-boehmite and 12.7 percent of silica sol by weight of dry basis, and the average particle size of the auxiliary agent is 79.8 mu m.

Example 7

This example analyzes the prepared adjuvant and compares it with the industrially used S-Zorb adsorbent FCAS-R09.

The basic conditions of the auxiliaries prepared are shown in Table 2.

Table 2 basic analytical data for auxiliaries

The comparative evaluation of the adsorbent and the auxiliary agent is shown in Table 3, and it can be seen that compared with the raw material, the octane number is lost by 0.6 point when the auxiliary agent is not added, the octane number loss is obviously reduced when different auxiliary agents are added, and the octane number of the product is also increased from 0.2 point of loss to 0.9 point of increase.

TABLE 3 comparative evaluation of adsorbents with adjuvants

The invention adopts modified ZSM-5, beta, mordenite or pure silicon molecular sieve, maintains or improves the octane number of the gasoline by isomerization and aromatization, is directly added into the reaction system of the prior S-Zorb process and is used together with the S-Zorb adsorbent, and can improve the octane number (RON) of the gasoline by more than 0.5 point.