CN107971040A - A kind of preparation method of catalytic cracking metal passivant and the matal deactivator prepared by this method - Google Patents
A kind of preparation method of catalytic cracking metal passivant and the matal deactivator prepared by this method Download PDFInfo
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- CN107971040A CN107971040A CN201610938210.4A CN201610938210A CN107971040A CN 107971040 A CN107971040 A CN 107971040A CN 201610938210 A CN201610938210 A CN 201610938210A CN 107971040 A CN107971040 A CN 107971040A
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- catalytic cracking
- bismuth
- metal passivant
- containing compound
- acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J33/00—Protection of catalysts, e.g. by coating
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of preparation method the invention discloses catalytic cracking metal passivant and the matal deactivator by this method preparation, this method include：A, antimony oxide, hydroxycarboxylic acid, boron-containing compound, bismuth-containing compound, pH adjusting agent and water are mixed, is reacted 30 60 minutes under conditions of being 20 90 DEG C in temperature, obtain the first product；B, oxidant is mixed with first product that step a is obtained, when reaction 12 is small in closed container under conditions of being 100 150 DEG C in temperature, obtains catalytic cracking metal passivant.Catalytic cracking metal passivant preparation method provided by the invention has the advantages that preparation process is simple, the reaction time is short, cost is low, reduces energy consumption, remarkable in economical benefits.The catalytic cracking metal passivant prepared by this method shows good passivation nickel, the function of vanadium when being used in catalytic cracking reaction, can be obviously improved light oil yield, reduce the ratio of coke and dry gas in product.
Description
Technical field
A kind of preparation method the present invention relates to catalytic cracking metal passivant and the catalytic cracking gold by this method preparation
Belong to passivator.
Background technology
In heavy oil catalytic cracking process, heavy metal (such as Ni, Fe, V, Cu) element in feedstock oil is constantly deposited on
On catalyst surface, the pollution of catalyst is caused.With being continuously increased for its deposition, the activity and selectivity band to catalyst
To adversely affect, decline petrol and diesel oil yield, hydrogen, coke yield rise.Metal passivation is added in catalytically cracked stock
Agent is to suppress the most economical effective method that heavy metal pollutes catalytic cracking catalyst.The inorganic antimony of matal deactivator early application
Salt, it is now more that passivator is made using organo-antimony compound, all achieve obvious passivation effect.The metallic blunt that the country uses at present
Agent is broadly divided into two classes, a kind of antimonial being dissolved in organic solvent；Another kind is the aqueous solution of antimonial.
Oil-soluble antimonial is more in early stage application.As Chinese patent CN87106236, United States Patent (USP) US4694324 are reported
Road on dihydroxy phosphordithiic acid antimony, when use, which must be first dissolved in organic solvent, can just use, and penetrating odor is stronger.
Water-soluble antimony passivator is the main Types applied at present, has conveying convenient, stability is good, non-stimulated smell, small toxicity etc.
Advantage.Chinese patent CN1245198A reports a kind of preparation method of passivator containing Sb, and effect is more single.Chinese patent
CN104028312A, CN104162455A report a kind of Sb base passivator containing rare earth element, can be blunt with bimetallic
Change acts on, but preparation process is complex.The preparation process of double-metal deactivator generally prepares two kinds of monometallics respectively at present
Then element passivator is formed, it is necessary to adjust the tenor in two kinds of matal deactivators by solvent complex, technique is cumbersome, and
The matal deactivator toxicity of production is high, stability is poor.
The content of the invention
Urged the object of the present invention is to provide a kind of preparation method of catalytic cracking metal passivant and by prepared by this method
Change cracking matal deactivator, to solve traditional preparation methods complex process, the problem of time consumption and energy consumption, product stability is poor.
To achieve these goals, first aspect present invention：A kind of preparation method of catalytic cracking metal passivant is provided,
This method includes：A, antimony oxide, hydroxycarboxylic acid, boron-containing compound, bismuth-containing compound, pH adjusting agent and water are mixed,
Temperature be 20-90 DEG C under conditions of react 30-60 minutes, obtain the first product, wherein, the antimony oxide, hydroxycarboxylic acid,
Boron-containing compound, bismuth-containing compound, the mass ratio of pH adjusting agent and water are 1：(2-4)：(0.5-1.2)：(0.4-2)：(0.6-
1.2)：(2-10)；B, oxidant is mixed with first product that step a is obtained, under conditions of temperature is 100-150 DEG C
When reaction 1-2 is small in closed container, catalytic cracking metal passivant is obtained, wherein, the oxidant and antimony oxide
Mass ratio is (0.4-1.1)：1.
Preferably, the boron-containing compound described in step a is boric acid and/or diboron trioxide.
Preferably, the bismuth-containing compound described in step a is at least one in bismuth oxide, bismuth hydroxide and bismuth nitrate
Kind.
Preferably, the pH adjusting agent described in step a is selected from monoethanolamine, diethanol amine, triethanolamine, ammonium hydroxide, phosphoric acid
At least one of sodium dihydrogen and disodium hydrogen phosphate.
Preferably, the hydroxycarboxylic acid described in step a is in tartaric acid, citric acid, lactic acid, malic acid and salicylic acid
At least one.
Preferably, the reaction described in step a carries out under agitation.
Preferably, the oxidant described in step b is selected from hydrogen peroxide, sodium peroxide, potassium peroxide and benzoyl peroxide first
At least one of acyl.
Preferably, the pH value for the catalytic cracking metal passivant that step b is obtained is 6-8.
Second aspect of the present invention：Also provide by the catalytic cracking metal passivant of the method preparation of first aspect present invention.
Through the above technical solutions, catalytic cracking metal passivant preparation method provided by the invention has preparation process letter
List, the reaction time is short, cost is low, reduces the advantages of energy consumption, remarkable in economical benefits.The catalytic cracking metal prepared by this method is blunt
Agent shows good passivation nickel, the function of vanadium when being used in catalytic cracking reaction, can be obviously improved light oil yield,
Reduce the ratio of coke and dry gas in product.In addition, catalytic cracking metal passivant provided by the invention also has good water
Dissolubility, can be miscible with water in any proportion, easy to use, and stability is strong, is not susceptible to flocculation depositional phenomenon, storage
Cycle is longer.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
First aspect present invention：A kind of preparation method of catalytic cracking metal passivant is provided, this method includes：A, by three
Two antimony, hydroxycarboxylic acid, boron-containing compound, bismuth-containing compound, pH adjusting agent and water mixing are aoxidized, in the bar that temperature is 20-90 DEG C
Reacted 30-60 minutes under part, obtain the first product, wherein, the antimony oxide, hydroxycarboxylic acid, boron-containing compound, bismuth-containing
The mass ratio of compound, pH adjusting agent and water is 1：(2-4)：(0.5-1.2)：(0.4-2)：(0.6-1.2)：(2-10)；B, by oxygen
Agent is mixed with first product that step a is obtained, and 1- is reacted in closed container under conditions of being 100-150 DEG C in temperature
2 it is small when, obtain catalytic cracking metal passivant, wherein, the mass ratio of the oxidant and antimony oxide is (0.4-1.1)：
1.It should be noted that since the catalytic cracking metal passivant prepared by the method for the present invention when in use generally can another external adding water
Used in form of an aqueous solutions after dissolving, so the water in the preparation method of catalytic cracking metal passivant provided by the present invention
Addition have no particular limits, be subject to and facilitate operation, such as the addition of water can be controlled in antimony oxide and water
Mass ratio be 1：In the range of (2-10).The method that first aspect present invention is provided, preparation process is simple, shorter anti-
Can be prepared between seasonable has the function of good passivation nickel, the catalytic cracking metal passivant of vanadium, in addition reaction need not pressurize,
Energy consumption thus can be reduced, remarkable in economical benefits.Under specific material rate react prepared catalytic cracking metal
Passivating agent products clear, has good water solubility, can be miscible with water in any proportion, and stability is strong, is not easy to send out
Raw flocculation depositional phenomenon, storage cycle are longer.
According to the first aspect of the invention, being used in catalytic cracking metal passivant of the invention formula has blunt nickel performance
Boron-containing compound and bismuth-containing compound instead of part antimony oxide, make product that there is environmental-protecting performance.Preferably, containing boronation
Compound can be boric acid and/or diboron trioxide.Bismuth-containing compound can be in bismuth oxide, bismuth hydroxide and bismuth nitrate
It is at least one.
According to the first aspect of the invention, the catalytic cracking metal passivant product of clear in order to obtain, prepared
Cheng Zhongxu adds pH adjusting agent to adjust the pH of reaction system, and the pH adjusting agent can be with weakly alkaline organic base or nothing
Machine alkali, the organic base are preferably alcohol amine compound, more preferably in monoethanolamine, diethanol amine and triethanolamine
It is at least one；The inorganic base is preferably selected from least one of ammonium hydroxide, sodium dihydrogen phosphate and disodium hydrogen phosphate.As the pH
When additive is ammonium hydroxide, the concentration of the ammonium hydroxide is preferably 10-30 mass %.
According to the first aspect of the invention, hydroxycarboxylic acid can further enhance the water of catalytic cracking metal passivant product
Dissolubility, makes passivator system stability stronger.The hydroxycarboxylic acid refers to that intramolecular includes the organic compound of hydroxyl and carboxyl,
It can include one or more hydroxyls, one or more carboxyls, it is however preferred to have 2-10 carbon atom, 1-4 hydroxyl and 1-4
Carboxyl, more preferably selected from least one of tartaric acid, citric acid, lactic acid, malic acid and salicylic acid.
According to the first aspect of the invention, in order to make antimony oxide in step a, hydroxycarboxylic acid, boron-containing compound, contain
Bismuth compound, pH adjusting agent and water are uniformly mixed to the full extent, can take mixed method well known to those skilled in the art,
Preferably, the reaction in step a can carry out under agitation.
According to the first aspect of the invention, antimony oxide can be oxidized to five with blunt nickel performance by addition oxidant
Aoxidize two antimony, the oxidant can be in for hydrogen peroxide, sodium peroxide, potassium peroxide and benzoyl peroxide at least
One kind, is preferably the hydrogen peroxide of 20-30 mass %.
According to the first aspect of the invention, the catalytic cracking metal passivant prepared by method provided by the present invention produces
Product are the solution of clear, and pH value is between 6-8, between preferably 7-8.
Second aspect of the present invention：Also provide by the catalytic cracking metal passivant of the method preparation of first aspect present invention.
The present invention will be further illustrated by embodiment below, but the present invention is not therefore subject to any restriction.
It is raw materials used in addition to special instruction in embodiment, it is chemically pure reagent.
Embodiment 1
1.8kg diethanol amine, 6kg tartaric acid, 3kg antimony oxides, 1.2kg bismuth oxides, 1.5kg boric acid and 30kg are gone
Ionized water is added in reaction kettle, after being stirred at room temperature 30 minutes, the hydrogen peroxide of 30 mass % of 2kg is added dropwise, adds rear closed reactor
And 100 DEG C of reaction 1h are heated to, kettle is then cooled down out, obtains catalytic cracking metal passivant, product clear, pH value is
7.1。
Embodiment 2
By 2.4kg monoethanolamines, 8kg citric acids, 2kg antimony oxides, 4kg bismuth hydroxides, 2.4kg boric acid and 4kg go from
Sub- water is added in reaction kettle, after being warming up to 90 DEG C of stirrings 30 minutes, 2.2kg benzoyl peroxides is added dropwise, add rear confined reaction
Kettle is simultaneously heated to 150 DEG C of reaction 1.5h after adding, and then cools down out kettle, obtains catalytic cracking metal passivant, product clarification is saturating
It is bright, pH value 8.0.
Embodiment 3
By 1.2kg triethanolamines, 3kg lactic acid, 1.2kg antimony oxides, 1.6kg bismuth nitrates, 0.8kg diboron trioxides and
7kg deionized waters are added in reaction kettle, and 50 DEG C of stirrings after sixty minutes, are added dropwise the hydrogen peroxide of 30 mass % of 2kg, add rear closed
Reaction kettle is simultaneously heated to 120 DEG C of reaction 1h, then cools down out kettle, obtains catalytic cracking metal passivant, product clear, pH
It is worth for 7.5.
Testing example 1
Embodiment 1-3 is tested for the property using the experiment of standard light oil micro-reactor, instrument is Sinopec oil
The exploitation manufacture of work research institute, test condition：500 DEG C of temperature, agent weight of oil is than 3, oil inlet quantity 1.388g.The raw material used
Oil is wax oil VGO, and 368,20 DEG C of density of relative molecular mass are 0.91g/cm3, Ni content 5.38ppm, V content 1.65ppm.
The composition analysis of micro-inverse product is measured using ASTM D7964 methods.
It is equilibrium catalyst for catalytic cracking process (the fully synthetic zeolite molecular sieve of rare-earth type that Yanshan Mountain refinery provides to test the catalyst used
Catalyst, its Ni content are 2000ppm, V content 600ppm).
After the deionized water of the embodiment 1-3 passivator requirements prepared is diluted, impregnation catalyst agent poising agent,
3h is bakeed at 700 DEG C again after 150 DEG C of drying 1h, it is respectively 1000,3000 and 3000ppm that Sb contents, which are prepared, and B content divides
Not Wei 100,700 and 700ppm, Bi content be respectively 400,5000 and 1900ppm test poising agent 1-3.
Conversion ratio, dry gas selectivity and coke selectivity are calculated according to the following formula.Test result is shown in Table 1.
Conversion ratio (%)=(dry gas+liquefied gas+gasoline+coke) yield/inlet amount × 100%
Dry gas selectivity (%)=dry gas yield/conversion ratio × 100%
Coke selectivity (%)=coking yield/conversion ratio × 100%
Test comparison example
It is with the difference of testing example, contrast poising agent used in this test comparison example is using certain business
What the Sb base passivator of brand was prepared.Test result is shown in Table 1.
Table 1
As can be seen from Table 1, the catalytic cracking metal passivant that prepared by the present invention is seasonable for Catalytic Cracking Unit of Measure, Ke Yiming
The aobvious selectivity for reducing dry gas and coke, is demonstrated by good passivation nickel, vanadium effect, further, it is also possible to be obviously improved light oil
Yield, reduces the ratio for reducing dry gas in product, hydrogen, heavy oil and coke.
Claims (9)
1. a kind of preparation method of catalytic cracking metal passivant, this method include：
A, antimony oxide, hydroxycarboxylic acid, boron-containing compound, bismuth-containing compound, pH adjusting agent and water are mixed, is in temperature
Reacted 30-60 minutes under conditions of 20-90 DEG C, obtain the first product, wherein, the antimony oxide, hydroxycarboxylic acid, containing boronation
Compound, bismuth-containing compound, the mass ratio of pH adjusting agent and water are 1：(2-4)：(0.5-1.2)：(0.4-2)：(0.6-1.2)：(2-
10)；
B, oxidant is mixed with first product that step a is obtained, in closed appearance under conditions of being 100-150 DEG C in temperature
When reaction 1-2 is small in device, catalytic cracking metal passivant is obtained, wherein, the mass ratio of the oxidant and antimony oxide is
(0.4-1.1)：1.
2. according to the method described in claim 1, wherein, the boron-containing compound described in step a is boric acid and/or three oxidations two
Boron.
3. according to the method described in claim 1, wherein, the bismuth-containing compound described in step a is selected from bismuth oxide, hydroxide
At least one of bismuth and bismuth nitrate.
4. according to the method described in claim 1, wherein, the pH adjusting agent described in step a is selected from monoethanolamine, diethanol
At least one of amine, triethanolamine, ammonium hydroxide, sodium dihydrogen phosphate and disodium hydrogen phosphate.
5. according to the method described in claim 1, wherein, the hydroxycarboxylic acid described in step a be selected from tartaric acid, citric acid,
At least one of lactic acid, malic acid and salicylic acid.
6. according to the method described in claim 1, wherein, the reaction described in step a carries out under agitation.
7. according to the method described in claim 1, wherein, the oxidant described in step b be selected from hydrogen peroxide, sodium peroxide,
At least one of potassium peroxide and benzoyl peroxide.
8. according to the method described in claim 1, wherein, the pH value for the catalytic cracking metal passivant that step b is obtained is
6-8。
9. the catalytic cracking metal passivant prepared as the method described in any one in claim 1-8.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115155667A (en) * | 2022-06-24 | 2022-10-11 | 淄博凯美可工贸有限公司 | Boron-based metal passivator and preparation method thereof |
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| US4595771A (en) * | 1984-11-16 | 1986-06-17 | Atlantic Richfield Company | Water-soluble antimony compounds and their preparation |
| CN102974399A (en) * | 2012-12-11 | 2013-03-20 | 江苏汉光实业股份有限公司 | Preparation method of catalytic cracking metal deactivator |
-
2016
- 2016-10-25 CN CN201610938210.4A patent/CN107971040B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4595771A (en) * | 1984-11-16 | 1986-06-17 | Atlantic Richfield Company | Water-soluble antimony compounds and their preparation |
| CN102974399A (en) * | 2012-12-11 | 2013-03-20 | 江苏汉光实业股份有限公司 | Preparation method of catalytic cracking metal deactivator |
Non-Patent Citations (1)
| Title |
|---|
| 丰华: "《石油加工助剂及石油产品添加剂加工配制与生产应用最新工艺技术操作手册 第1卷》", 30 June 2006, 中国科技文化出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115155667A (en) * | 2022-06-24 | 2022-10-11 | 淄博凯美可工贸有限公司 | Boron-based metal passivator and preparation method thereof |
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