CN100496712C - Oil deacidfying catalyst and method thereof - Google Patents

Oil deacidfying catalyst and method thereof Download PDF

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CN100496712C
CN100496712C CNB2005100678646A CN200510067864A CN100496712C CN 100496712 C CN100496712 C CN 100496712C CN B2005100678646 A CNB2005100678646 A CN B2005100678646A CN 200510067864 A CN200510067864 A CN 200510067864A CN 100496712 C CN100496712 C CN 100496712C
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oil
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family metal
crude oil
accordance
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CN1854259A (en
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祝馨怡
田松柏
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China Petroleum and Chemical Corp
China Petrochemical Corp
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Abstract

It is a kind of oil deacidification catalyst that contains 99.2%-99.9% IIA metal oxide and 0.1%-0.8% IA metal inorganic salt in weight. The method of preparing this catalyst is dipping the IIA metal oxide in the solution of IA metal inorganic salt, then drying and roasting. It is useful for depriving the naphthenic acid of oil in the lower temperature with this kind of catalyst, besides; this can make the acid value of oil greater drop in yield.

Description

A kind of oil product deacidifying catalyst and acid stripping method
Technical field
The present invention is a kind of oil product deacidifying catalyst and acid stripping method, specifically, is a kind ofly to reduce the catalyst of oil or distillate acid number and use this catalyst to reduce the method for described oil product acid number.
Background technology
Because density, viscosity and the acid number of heavy acid-containing raw oil are higher, in process, can cause bigger corrosion to equipment, cause the maintenance of equipment maintenance frequent, problems such as product quality decline, contaminated environment, many refineries lack the ability of processing highly acid crude oil, therefore drug on the market to cause on the market high-acid crude oil, and price is lower.The measure corrosive commonly used that reduces acid-containing raw oil has three kinds: a kind of is with high-acid crude oil and low sour crude oil blending, but the latter's price is more much higher than the former, uneconomical on the cost, but also will be subjected to the restriction of low sour oil supply amount and petroleum tank reserves.Another kind is the erosion-resisting expensive alloy material of a large amount of uses in refining equipment and device, so not only improved cost of investment greatly, and concerning existing oil refining apparatus, the anticorrosive that more renews is also unrealistic.The third is to add corrosion inhibiter in crude oil, but corrosion inhibiter can influence follow-up catalysis process, reduces activity of such catalysts and life-span, and is also influential to the quality of oil product.
The acid number of crude oil is the total amount of various acidic components in the crude oil, comprises aphthenic acids, aliphatic acid, aromatic acid, inorganic acid, mercaptan, hydrogen sulfide, phenol etc., and is wherein the highest with naphthenic acid content.The corrosion of process equipment is mainly caused by aphthenic acids.Therefore, remove or reduce naphthenic acid content in the crude oil as far as possible, just can significantly reduce the corrosivity of acid-containing raw oil.Existing high-acid crude oil acid stripping method mainly contains alkali neutralisation, solvent extraction process, absorption method, aphthenic acids esterification or amidatioon, hydrogenation method etc.These methods all exist various defectives when effectively reducing acid value for crude oil.As alkaline cleaning procedure serious emulsion takes place, and produce a large amount of waste residues, environmental pollution is serious, and control expense is high; Solvent extraction and adsorption method of separation technological process complexity, the energy consumption height, investment is big and be not suitable for the heavy crude depickling; The aphthenic acids conversion reaction needs a large amount of organic amine or alcohol to make raw material, and cost is higher, the last handling process complexity, and react the ester of generation or acid amides is produced acid in addition by the reversible reaction hydrolysis possibility; Though hydrogenation method can thoroughly remove the aphthenic acids in the crude oil, a large amount of hydrogen of reaction needed, technology construction investment and running cost are higher.
High-acid crude oil is except that the acid number height, and viscosity is also bigger usually, is unsuitable for pipeline transportation.If before transportation, carry out the depickling visbreaking, just can reduce cost of transportation greatly.Above-mentioned acid stripping method is because the variety of issue of its existence is difficult to also at present realize that well head crude oil is carried out depickling to be handled.For conveniently being used for well head crude oil deacidification visbreaking, the best way is to utilize hot-working method that aphthenic acids is decomposed to reduce acid value for crude oil and viscosity.
USP5, employing heat-treating methods such as 820,750, USP5,976,360, USP6,086,751 decomposes carboxylic acid, generates CO, CO 2And H 2O etc.This process is simple, but will obtain higher acid removal rate, needs higher heating-up temperature, and need remove the water in the crude oil in advance.The high-temperature heat treatment depickling tends to cause crude oil pyrolysis, coking, the composition of destruction crude oil.
For solving the coking of crude oil deacidification process and improving acid removal rate, USP4,642,175, USP5,055,175, USP5,688,395, USP5,914,030, USP5,928,502 grades propose in reaction raw materials, to add expensive oil-soluble or in oil dispersible metallic compound as catalyst, as USP5, metallic compound in 928,502 catalyst system therefors is selected from the compound of VB, VIB, VIIB or VIII family metal, and its use amount is at least 5wppm in amount of metal.
Said process depickling reaction is reaction of high order, generates water, CO and CO in the course of reaction 2, must reduce H in the reaction system as far as possible 2O amount, and control CO and CO 2Amount could improve deacidification efficiency.Therefore before heat treatment, need the water flash distillation is removed, also need keep lower H during reaction with a large amount of inert gas purge reaction systems 2O, CO, CO 2The dividing potential drop sum, the volatile component that forms in heat treatment process must reclaim.These have all improved operating cost greatly.
USP5,985,137 add the alkaline earth oxide of capacity in crude oil, be mainly calcium oxide or barium monoxide, make it under heating condition with crude oil in the aphthenic acids reaction generate the carbonate of alkaline-earth metal, again this carbonate is separated with crude oil, can reduce the acid number of crude oil.USP6,679,987B 1The naphthenate, oxide, the hydroxide that then add IA or IIA family metal in acid-containing raw oil reduce the acid number of crude oil.When it uses the metallic compound depickling of IIA family, need to carry out the depickling reaction again after the adding low amounts of water, then do not need to add water when using IA family metallic compound and can carry out the depickling reaction.
[Applied Catalysis A:General, 83 (1992) 165-178] such as Seung Jun Lee disclose a kind of heterogeneous catalysis of methyl formate decarbonylation base, with various sylvite, are mainly KCl, K 2SO 4, K 2CO 3Load on the carriers such as active carbon, silica, magnesia, aluminium oxide and make catalyst.Wherein contain more KCl in the catalyst that load KCl makes on magnesia, its content is 1～10wt%, otherwise catalytic activity is extremely low.
Summary of the invention
The purpose of this invention is to provide a kind of oil product deacidifying catalyst and use this catalyst to carry out the method for oil product depickling.
Oil product deacidifying catalyst provided by the invention comprises the inorganic salts of the IA family metal of the IIA family metal oxide of 99.2～99.9 quality % and 0.1～0.8 quality %.
Oil product acid stripping method provided by the invention is included in the catalyst of the present invention that adds its gross mass 0.1～1.0% in the oil product, makes oil product 100～400 ℃ of fully reactions in closed container.
The present invention loads on the inorganic salts of IA family metal on the IIA family metal oxide and makes catalyst, using this catalyst to carry out crude oil deacidification handles, can reduce the depickling reaction temperature greatly, thereby effectively avoid crude oil pyrolysis and coking in the deacidification, and suitably reduce oil viscosity.In addition, the inventive method depickling reaction is decarboxylic reaction, is subjected in the system influence of water content little, and a spot of water does not need to remove in advance in the crude oil, so technology is simple, and operating cost is low.
The specific embodiment
The present invention loads on the inorganic salts of an amount of IA family metal on the IIA family metal oxide and makes catalyst, and uses this catalyst to react under relatively low reaction temperature, makes the carboxylic acid generation decarboxylic reaction in the oil product, thereby reduces the oil product acid number.
In the described catalyst, the IIA family metal oxide is a catalyst carrier, and the IIA family metal oxide is selected from BeO, MgO, CaO, SrO or BaO, preferred magnesia or calcium oxide.The inorganic salts of IA family metal are its hydrochloride, nitrate, sulfate or carbonate in the catalyst, and the inorganic salts of preferred IA family metal are potassium chloride, potassium nitrate, potassium sulfate or potash.The amount of the inorganic salts of IA family metal should be limited in the scope of the present invention's regulation in the catalyst.Inorganic salt content described in the catalyst is low excessively, will influence activity of such catalysts, and the deacidification effect of too high levels catalyst also can descend.
Catalyst provided by the invention can adopt the preparation of physical mixed method, also can adopt the dipping method preparation, and the preparation method of dipping comprises the inorganic salt solution dipping IIA family metal oxide with IA family metal, dry then, roasting.
The preferred magnesia of described IIA family metal oxide, the preferred potassium chloride of inorganic salts, potassium nitrate, potassium sulfate or the potash of IA family metal.
In the described infusion process, be 40～90 ℃ with the dipping temperature of the inorganic salt solution of IA family metal dipping IIA family metal oxide, preferred 60～80 ℃.The inorganic salt concentration that uses during dipping is 0.01～0.1 mol, preferred 0.01～0.05 mol.Gu liquid/than being 1～5 milliliter/gram, suitable dip time is 1～8 hour.
In the described method, with being dried behind the inorganic salt solution impregnated carrier, and then roasting.Baking temperature is 100～120 ℃, and the time is 1～12 hour, preferred 2～6 hours.The roasting of catalyst needs to decide according to used inorganic salts type, and sintering temperature should not be higher than the decomposition temperature of inorganic salts.Particularly, when used inorganic salts were potassium chloride or potassium sulfate, the sintering temperature behind the dipping was 500～800 ℃, and when used inorganic salts were potassium nitrate or potash, the sintering temperature behind the dipping was 200～500 ℃.Suitable roasting time is 2～8 hours.
Oil product acid stripping method provided by the invention is to make to contain sour oil product carry out the petroleum acids decarboxylic reaction in the presence of catalyst of the present invention in airtight container, thereby the acid number of oil product is reduced.0.2～0.5% of the preferred oil product gross mass of catalytic amount that adds in the depickling reaction.Preferred 200～350 ℃ of reaction temperature, the suitable reaction time is 30～120 minutes.
The oil product that is suitable for carrying out with the inventive method depickling can be crude oil or distillate, described crude oil can be the crude oil without any processing, also can be the crude oil of dewatering and desalting or remove water and the topped crude of lighter hydrocarbons that described distillate is gasoline, diesel oil, kerosene, wax oil, reduced crude or decompression residuum.
Below by example in detail the present invention, but the present invention is not limited to this.
The standard method (ASTM-D664) that acid value for crude oil adopts constant-current titration to measure the oil product acid number in the example is measured.
Example 1
With 20 gram MgO powder 700 ℃ of roastings 4 hours, to wherein adding the KCl solution that 27 ml concns are 0.03 mol, 80 ℃ of continuous stirring 8 hours, 120 ℃ of dryings 4 hours, 600 ℃ of roastings 2 hours, catalyst B.KCl content is 0.3 quality % in the catalyst B, and MgO content is 99.7 quality %.
Example 2
Method by example 1 prepares catalyst C, and different 27 ml concns that are to use are the K of 0.015 mol 2SO 4Solution impregnation MgO, K among the catalyst C that obtains 2SO 4Content is 0.35 quality %, and MgO content is 99.65 quality %.
Example 3
Method by example 1 prepares catalyst D, and different 27 ml concns that are to use are the K of 0.015 mol 2CO 3Solution impregnation MgO is behind the impregnation drying, in 400 ℃ of roastings 2 hours.K among the catalyst D 2CO 3Content is 0.28 quality %, and MgO content is 99.72 quality %.
Example 4
Method by example 1 prepares catalyst E, and different 27 ml concns that are to use are the KNO of 0.03 mol 3Solution impregnation MgO is behind the impregnation drying, in 400 ℃ of roastings 2 hours.KNO among the catalyst E 3Content is 0.4 quality %, and MgO content is 99.6 quality %.
Example 5
Method by example 1 prepares catalyst F, and different 27 ml concns that are to use are the KCl solution impregnation MgO of 0.05 mol, and KCl content is 0.5 quality % among the catalyst F that obtains, and MgO content is 99.5 quality %.
Comparative Examples 1
With 700 ℃ of roastings of 20 gram MgO powder 4 hours, obtain catalyst A.
Example 6～11
The deacidification effect of following case expedition catalyst of the present invention.
In the stainless steel autoclave of 1 liter of band agitating device, the adding acid number is that 12.18mgKOH/g, viscosity are 823.5mm 2The Sudan Fula-1B crude oil without dehydration, desalination of/s (50 ℃) adds the catalyst account for crude oil total amount 0.5 quality %, under the airtight condition in 350 ℃ of stirring reactions 2 hours.React the mensuration acid value for crude oil that finishes, calculate the crude oil deacidification rate, viscosity of crude sees Table 1 after each example catalyst system therefor, acid removal rate and the depickling.Acid removal rate is the percentage of acid value for crude oil before depickling reaction front and back acid value for crude oil difference and the depickling in the table 1.
As shown in Table 1, catalyst of the present invention has higher acid removal rate than the comparative catalyst, and the viscosity of depickling processing back crude oil descends to some extent.
Example 12～18
Following case expedition depickling reaction temperature and catalyst dosage are to depickling result's influence.
Get catalyst B, press the method for example 6, but change the temperature and the catalyst dosage of crude oil deacidification reaction, each example crude oil deacidification reaction result sees Table 2.
Example 19～22
Investigate the effect of using catalyst of the present invention different crude oils to be carried out depickling.
Press the method for example 6, use catalyst B that the crude oil without dehydration, desalination with different acid numbers is carried out depickling and handle, used acid value for crude oil of each example and depickling the results are shown in Table 3.
Table 1
Instance number The catalyst numbering Acid removal rate, quality % Viscosity of crude after the depickling (50 ℃), mm 2/s
6 A 78.6 345.4
7 B 91.8 93.05
8 C 82.6 297.8
9 D 82.7 286.1
10 E 83.1 263.2
11 F 79.6 328.7
Table 2
Instance number The catalyst dosage, quality % Reaction temperature, ℃ Acid removal rate, quality %
12 0.5 200 72.8
13 0.5 250 85.3
14 0.5 300 89.6
15 0.1 350 81.9
16 0.3 350 87.2
17 0.5 350 91.8
18 0.8 350 91.6
Table 3
Figure C200510067864D00081

Claims (11)

1, a kind of oil product deacidifying catalyst comprises the inorganic salts of the IA family metal of the IIA family metal oxide of 99.2～99.9 quality % and 0.1～0.8 quality %.
2, according to the catalyst of claim 1, it is characterized in that the IIA family metal oxide is a magnesia, the inorganic salts of IA family metal are potassium chloride, potassium nitrate, potassium sulfate or potash.
3, the described Preparation of catalysts method of a kind of claim 1 comprises the inorganic salt solution dipping IIA family metal oxide with IA family metal, dry then, roasting.
4, in accordance with the method for claim 3, it is characterized in that described IIA family metal oxide is a magnesia, the inorganic salts of IA family metal are potassium chloride, potassium nitrate, potassium sulfate or potash.
5, according to claim 3 or 4 described methods, Gu liquid when it is characterized in that flooding/than being 1～5 milliliter/gram, dipping temperature is 40～90 ℃.
6, in accordance with the method for claim 4, when it is characterized in that described inorganic salts are potassium chloride or potassium sulfate, the sintering temperature behind the dipping is 500～800 ℃, and when described inorganic salts were potassium nitrate or potash, the sintering temperature behind the dipping was 200～500 ℃.
7, a kind of oil product acid stripping method is included in the oil product and adds the described catalyst of claim 1 that accounts for its gross mass 0.1～1.0%, makes oil product 100～400 ℃ of fully reactions in closed container.
8, in accordance with the method for claim 7, it is characterized in that the catalytic amount that adds is 0.2～0.5% of an oil product gross mass.
9, in accordance with the method for claim 7, it is characterized in that described reaction temperature is 200～350 ℃, the reaction time is 30～120 minutes.
10, in accordance with the method for claim 7, it is characterized in that described oil product is crude oil or distillate.
11, in accordance with the method for claim 10, it is characterized in that described crude oil for without the crude oil of the crude oil of any processing, dewatering and desalting or remove water and the topped crude of lighter hydrocarbons, described distillate is gasoline, diesel oil, kerosene, wax oil, reduced crude or decompression residuum.
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CN101574647B (en) * 2009-04-23 2011-06-01 中国海洋石油总公司 Preparation method of ultra-deep absorption desulfurization and denitrogenation agent for hydrocracking tail oil
CN101766997B (en) * 2010-01-09 2012-05-02 高忠武 Catalyst for removing organic acid in oil and preparation method thereof
CN108620137B (en) * 2017-03-15 2021-03-19 成都汇嘉春天科技有限公司 Preparation process of catalyst for deacidifying organic compound

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