CN101391213A - Catalyst capable of removing petroleum acid in oil product and application method thereof - Google Patents
Catalyst capable of removing petroleum acid in oil product and application method thereof Download PDFInfo
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- CN101391213A CN101391213A CNA2007101220225A CN200710122022A CN101391213A CN 101391213 A CN101391213 A CN 101391213A CN A2007101220225 A CNA2007101220225 A CN A2007101220225A CN 200710122022 A CN200710122022 A CN 200710122022A CN 101391213 A CN101391213 A CN 101391213A
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Abstract
Disclosed is an oil catalytic deacidification catalyst, and the catalyst contains alkaline earth metal oxides, contains or does not contain transition metal oxides; and the alkaline earth metal oxides and the transition metal oxides are nanometer materials. The deacidification catalyst has high deacidification activity, and can particularly remove small molecular naphthenic acid in oil products selectively.
Description
Technical field
The present invention relates to a kind of catalyst and application process thereof that removes the acid of oil product PetroChina Company Limited..
Background technology
Along with the exhausted day by day and oil recovery technique of petroleum resources improves constantly, the crude oil production scope constantly enlarges, and the output of crude oil with high acid value increases year by year.The too high meeting of acid value for crude oil causes serious corrosion to refining equipment, influences the long period safe handling of oil refining apparatus, increases processing cost, and causes the acid number height of oil product, influences the use of oil product.
Acid in the crude oil comprises aphthenic acids, aliphatic acid, aromatic acid, inorganic acid, mercaptan, hydrogen sulfide and phenol etc., and wherein the content of aphthenic acids accounts for 90%, mainly is to be caused by aphthenic acids to the corrosion of process equipment.The corrosion of aphthenic acids is normal relevant with the activity of aphthenic acids, and with the increase of molecular weight, number of rings increases in the molecular structure, and the chemical reaction ability of aphthenic acids and metal can reduce gradually, thereby the activity of aphthenic acids reduces with the increase of molecular weight.The corrosivity difference of the aphthenic acids of different molecular weight, molecular weight is easy to form oil-soluble iron naphthenate less than 450 aphthenic acids, has stronger corrosivity.And molecular weight is not easy to form the oil-soluble iron naphthenate greater than 450 aphthenic acids, and corrosivity is very weak.
At present, the production technology of acid-containing raw oil and distillate decylization alkanoic acid mainly comprises: chemical extraction method, adsorption method of separation, solvent extraction process, esterification deacidification method, catalytic hydrogenation depickling method, hot depickling, catalyse pyrolysis depickling method etc.The catalyse pyrolysis depickling is to add catalyst in oil product, promotes the petroleum acids decarboxylation, can under lower reaction temperature, react, and the acid removal rate height.
Announced among the patent CN1272869A that under the condition that does not have hydrogen to exist at 204～426 ℃, atmospheric pressure 15～1000psi keeps water and CO with the catalyst of the oil-soluble of VB, VIB, VIIB, VIII family metal or oil-dispersing property metallic compound
2Merge under the condition that dividing potential drop is lower than 50psi crude oil or distillate are carried out catalytic decarboxylation.
Having announced among the U.S. Patent Publication No. US2006016723A1 combines with alkaline earth oxide, transition metal oxide and clay absorbents such as rare-earth oxide and kaolin carries out catalytic decarboxylation reaction to crude oil, reaction temperature is 200～450 ℃, and reaction system can be sealed glass tube, autoclave, flow reactor, batch reactor, slurry phase reactor and their combination etc.
Patent CN1827744A has announced a kind of method of processing crude oil with high acid value, be to make pretreated total acid number after preheating, inject fluid catalytic cracking reactor to contact with catalyst greater than the crude oil of 0.5mgKOH/g, and under the catalytic cracking reaction condition, react, oil gas behind the separating reaction and catalyst, reaction oil gas is delivered to subsequent separation system, and reacted catalyst recycles after stripping, regeneration.Described catalyst adopts any catalyst that is applicable to the FCC process, preferably contains one or more the catalyst in alkaline-earth metal, IVB family metal, group vib metal, VIIB family metal, the VIII family metal.
CN1854259A has announced 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 %.This Preparation of catalysts method comprises the inorganic salt solution dipping IIA family metal oxide with IA family metal, dry then, roasting.
CN 1903991A has announced a kind of catalytic deacidification method of hydrocarbon raw material, comprise described hydrocarbon feed 100～300 ℃ and deacidifying catalyst haptoreaction, described deacidifying catalyst comprises calcium oxide and calcium sulfate, and wherein the mass ratio of calcium oxide and calcium sulfate is 0.1～2.0.
The hot acid stripping method of existing catalysis removes aphthenic acids all in the crude oil, and catalyst consumption is big, the process conditions harshness, and the depickling activity of catalyst remains further to be improved.
Summary of the invention
The technical problem to be solved in the present invention provides the higher deacidifying catalyst of a kind of activity.Another object of the present invention provides a kind of method that removes aphthenic acids in the oil product.
The invention provides a kind of oil product catalytic deacidification catalyst, described catalyst contains alkaline earth oxide, contains or do not contain transition metal oxide; Described alkaline earth oxide and transition metal oxide are nano material.
The invention provides a kind of method that removes the acid of oil product PetroChina Company Limited., comprise the step that oil product and catalyst are contacted under the condition of heating, it is characterized in that, described catalyst is catalyst that the invention described above provided.
Catalyst of the present invention has that nanocrystal, aperture are suitable, specific area is big, and depickling is active high, especially low-molecular-weight aphthenic acids is had the very high activity that removes; Acid stripping method of the present invention can remove the aphthenic acids in the oil product, especially can the medium and small molecular naphthenic acid of selectively removing oil product.For example, the present invention is 5mgKOH/g by the catalyst of 60 weight % nano magnesias, 40 weight % nano-sized iron oxides preparation with the acid number, and wherein molecular weight is that 17.7% dewatering and desalting crude oil is raw material less than 450 naphthenic acid content, at 300 ℃ of reaction temperatures, water and CO
2Merging dividing potential drop 200K Pa, weight (hourly) space velocity (WHSV) 10h
-1Condition under carry out depickling reaction, acid removal rate is 60%, after the depickling in the oil product molecular weight be 6.2% less than 450 naphthenic acid content; And by the catalyst of the conventional iron oxide preparation of 60 weight % light calcined magnesias, 40 weight %, under similarity condition, carry out instead, acid removal rate is 10%, after the depickling in the oil product molecular weight be 13.6% less than 450 naphthenic acid content.
The specific embodiment
Nano material is meant the ultra-micro powder of the particle size of material less than 100nm.
Nano material of the present invention, preferably its average grain diameter is 4～90nm, specific area is 50～200m
2/ g, the aperture is 50～200 dusts.
In the catalyst provided by the present invention, be benchmark with the weight of catalyst, in oxide, the content of alkaline-earth metal is 60～100 heavy %, and preferred 75～95 heavy %, the content of transition metal are 0～40 heavy %, preferred 5～25 heavy %.
In the catalyst provided by the present invention, described alkaline earth oxide is selected from MgO, CaO or their mixture, described transition metal oxide is preferably one or more of Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, Zn, rare-earth oxide, and described rare-earth oxide is preferably the oxide into La and/or Ce.Described nano-oxide can be commercially available or according to existing method preparation, for example nano magnesia can be according to the method preparation in the document " the synthetic and sign of novel bitter earth nano band coprecipitation " (Chinese Journal of Inorganic Chemistry, 2005,21 (6)).
Acid number (TAN) be in and the total amount of the KOH that various acidic components consumed in the 1g crude oil, represent (referring to the ASTMD-664 method) with mgKOH/g.
In the method that removes petroleum acids of the present invention, described oil product is contacted with catalyst, the temperature of contact is 200～380 ℃, is preferably 300～350 ℃, and weight (hourly) space velocity (WHSV) is 0.1～50hr
-1, water and CO
2The merging dividing potential drop be no more than 350K Pa, preferably be no more than 200KPa, more preferably no more than 100KPa.
The method of the invention can be used for removing the petroleum acids in the oil product, and described oil product is one or more in crude oil, the fraction oil of petroleum, and for example desalting and dewatering contains acid or high-acid crude oil, diesel oil, decompressed wax oil.
The present invention is further illustrated for the following examples, but therefore do not limit the present invention.Raw materials used character sees Table 1 in embodiment and the Comparative Examples, and wherein aperture and specific area are recorded by the BET method; The crystallite dimension of catalyst is recorded by xrd method.
Table 1
| Material name | Nano-MgO | Nanometer CaO | Nanometer Ag 2O | Nanometer Fe 2O 3 | Nanometer Cr 2O 3 | Light-burned MgO | Fe 2O 3 |
| Average pore size, the method preparation | Press 1. method preparation of document | Press 1. method preparation of document | Press 1. method preparation of document | Press 1. method preparation of document | Tianjin reagent company | Beijing reagent company |
1. " the synthetic and sign of novel bitter earth nano band coprecipitation ", Chinese Journal of Inorganic Chemistry, 2005,21 (6).When the nano-oxide of other element of preparation, react with the nitrate of respective element replacement magnesium nitrate.
Embodiment 1
The 10g nano magnesia is broken into 10～20 orders through compression molding, is designated as C-1, forms to see Table 2.
Embodiment 2
9.0g nano calcium oxide, the 1.0g nano chromium oxide, mechanical mixture is even, and compression molding is broken into 10～20 orders, is designated as C-2, forms to see Table 2.
Embodiment 3
7.0g nano magnesia, the 1.0g nano calcium oxide, the 2.0g nano phase ag_2 o fully mixes, and compression molding is broken into 10～20 orders, is designated as C-3, forms to see Table 2.
Embodiment 4
6.0g nano magnesia, the 4.0g nano-sized iron oxide behind abundant mixed-forming, is broken into 10～20 orders, is designated as C-4, forms to see Table 2.
Comparative Examples 1
The 10g light calcined magnesia, compression molding is broken into 10～20 orders, is designated as D-1, and its composition sees 2.
Comparative Examples 2
6.0g light calcined magnesia, the 4.0g iron oxide behind abundant mixed-forming, is broken into 10～20 orders, is designated as D-2, forms to see Table 2.
Table 2
Embodiment 5
On the fixed-bed micro-reactor of a continuous feed catalyst is estimated, raw materials used is that acid number is 7.5 Yanshan Mountain AGO oil (Yanshan Petrochemical provides), and catalyst is C-1, and loadings is 10g, and reaction temperature is 350 ℃, and weight (hourly) space velocity (WHSV) is 8hr
-1, keep water and CO with the nitrogen purging
2The merging dividing potential drop be 100kPa.Its acid number of crude oil sample analysis of 8.0～9.0 hours, the content of little molecular naphthenic acid are answered in negate, and the corrosion test data.
Embodiment 6
Evaluating apparatus, loaded catalyst, sample time and analysis content are with embodiment 5.Raw materials used is that acid number is 7.5 Yanshan Mountain AGO, and with embodiment 5, catalyst is C-4, and reaction temperature is 300 ℃, and weight (hourly) space velocity (WHSV) is 45hr
-1, keep water and CO with the nitrogen purging
2The merging dividing potential drop be 100kPa.
Embodiment 7
Evaluating apparatus, loaded catalyst, sample time and analysis content are with embodiment 5.Raw materials used is that acid number is 7.5 Yanshan Mountain AGO, and with embodiment 5, catalyst is C-1, and reaction temperature is 350 ℃, and weight (hourly) space velocity (WHSV) is 20hr
-1, keep water and CO with the nitrogen purging
2The merging dividing potential drop be 100kPa.
Embodiment 8
Evaluating apparatus, loaded catalyst, sample time and analysis content are with embodiment 5.Raw materials used with embodiment 5, catalyst is C-2, and reaction temperature is 250 ℃, and weight (hourly) space velocity (WHSV) is 2hr
-1, keep water and CO with the nitrogen purging
2The merging dividing potential drop be 150kPa.
Embodiment 9
Evaluating apparatus, loaded catalyst, sample time and analysis content are with embodiment 5.Raw materials used is that acid number is 5.0 dewatering and desalting crude oil, and catalyst is C-3, and loadings is 10g, and reaction temperature is 350 ℃, and weight (hourly) space velocity (WHSV) is 15hr
-1, keep water and CO with the nitrogen purging
2The merging dividing potential drop be 300kPa.
Embodiment 10
Evaluating apparatus, loaded catalyst, sample time and analysis content are with embodiment 5.Raw materials used is that acid number is 5.0 dewatering and desalting crude oil, and with embodiment 9, catalyst is C-4, and reaction temperature is 300 ℃, and weight (hourly) space velocity (WHSV) is 10hr
-1, keep water and CO with the nitrogen purging
2The merging dividing potential drop be 200kPa.
Comparative Examples 3
Evaluating apparatus, sample time and analysis content are with embodiment 5.Raw materials used with embodiment 5, catalyst is D-1, and reaction temperature is 350 ℃, and weight (hourly) space velocity (WHSV) is 8hr
-1, keep water and CO with the nitrogen purging
2The merging dividing potential drop be 100kPa.
Comparative Examples 4
Evaluating apparatus, sample time and analysis content are with embodiment 5.Raw materials used is that acid number is 5.0 dewatering and desalting crude oil, and with embodiment 9, catalyst is D-2, and reaction temperature is 300 ℃, and weight (hourly) space velocity (WHSV) is 10hr
-1, keep water and CO with the nitrogen purging
2The merging dividing potential drop be 200kPa.
Table 3
| The embodiment numbering | 5 | 6 | 7 | 8 | 9 | 10 | Comparative Examples 3 | Comparative Examples 4 |
| The catalyst numbering | C-1 | C-4 | C-1 | C-2 | C-3 | C-4 | D-1 | D-2 |
| Raw material | Yanshan Mountain AGO | Yanshan Mountain AGO | Yanshan Mountain AGO | Yanshan Mountain AGO | Dewatering and desalting crude oil | Dewatering and desalting crude oil | Yanshan Mountain AGO | Dewatering and desalting crude oil |
| Raw material acid number TAN | 7.5 | 7.5 | 7.5 | 7.5 | 5 | 5 | 7.5 | 5 |
| Reaction temperature, ℃ | 300 | 300 | 350 | 250 | 350 | 300 | 300 | 300 |
| Weight (hourly) space velocity (WHSV), hr -1 | 8 | 45 | 20 | 2 | 15 | 10 | 8 | 10 |
| Water and CO 2The merging dividing potential drop, kPa | 100 | 100 | 100 | 150 | 300 | 200 | 100 | 200 |
| 8～9hr collects the acid number TAN of liquid | 1.5 | 0.15 | 0 | 3.2 | 1.25 | 2 | 2.25 | 4.5 |
| Acid removal rate, % | 80 | 98 | 100 | 57.3 | 75 | 60 | 30 | 10 |
| Molecular weight accounts for total aphthenic acids amount, w% less than 450 aphthenic acids | 15 | 2 | 0 | 42.7 | 3.5 | 6.2 | 58 | 13.6 |
| 280 ℃ of relative corrosion rates, ω (Fe)/μ gg -1 | 294 | 29 | 0 | 627 | 103 | 221 | 441 | 520 |
Annotate: molecular weight is 100% less than 450 naphthenic acid content in the AGO raw material of the used Yanshan Mountain.
Molecular weight does not account for 17.7% of total aphthenic acids amount less than 450 aphthenic acids in the depickling crude oil.
The TAN of acid removal rate=(TAN of oil sample is collected in the TAN-reaction back of raw material) * 100/ raw material.
The molecular weight determination of aphthenic acids adopts mass spectrography in the oil product.
The method of corrosion test is the iron powder corrosion test, and the concentration of iron ion is high more, and the expression corrosion is severe more.Its method is seen " corrosivity that the iron powder etch is estimated petroleum acids ", Zhang Lei etc., petroleum refining and chemical industry, 2006,37 (11), 58～61.
Claims (8)
1, a kind of oil product catalytic deacidification catalyst, described catalyst contains alkaline earth oxide, contains or do not contain transition metal oxide; Described alkaline earth oxide and transition metal oxide are nano material.
According to the described catalyst of claim 1, it is characterized in that 2, the average grain diameter of described nano material is 4～90nm, specific area is 50～200m
2/ g, average pore size is 50～200 dusts.
3, according to the described catalyst of claim 1, it is characterized in that, is benchmark with the weight of catalyst, and in oxide, the content of alkaline-earth metal is 60～100 heavy %, and the content of transition metal is 0～40 heavy %.
According to the described catalyst of claim 1, it is characterized in that 4, described alkaline earth oxide is MgO and/or CaO; Described transition metal is one or more in Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, Zn, the rare earth metal.
According to the described catalyst of claim 4, it is characterized in that 5, described rare earth metal is La and/or Ce.
6, a kind of method that removes the acid of oil product PetroChina Company Limited. comprises the step that oil product is contacted with catalyst, it is characterized in that, described catalyst is each described catalyst of claim 1～5.
7, in accordance with the method for claim 6, it is characterized in that the temperature of described contact is 200～380 ℃, weight (hourly) space velocity (WHSV) is 0.1～50hr
-1, purging with nitrogen, the merging dividing potential drop of control water and carbon dioxide is no more than 350KPa.
8, in accordance with the method for claim 6, it is characterized in that described temperature is 300～350 ℃, the merging dividing potential drop of described water and carbon dioxide is no more than 200KPa.
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|---|---|---|---|
| CNA2007101220225A CN101391213A (en) | 2007-09-20 | 2007-09-20 | Catalyst capable of removing petroleum acid in oil product and application method thereof |
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| CNA2007101220225A CN101391213A (en) | 2007-09-20 | 2007-09-20 | Catalyst capable of removing petroleum acid in oil product and application method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104492412A (en) * | 2015-01-07 | 2015-04-08 | 李�杰 | Preparation method of petroleum deacidification catalyst |
| CN106277414A (en) * | 2015-05-18 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of oil-polluted water eliminates the method for foam |
| CN108620137A (en) * | 2017-03-15 | 2018-10-09 | 成都汇嘉春天科技有限公司 | The preparation process of organic compound depickling catalyst |
-
2007
- 2007-09-20 CN CNA2007101220225A patent/CN101391213A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104492412A (en) * | 2015-01-07 | 2015-04-08 | 李�杰 | Preparation method of petroleum deacidification catalyst |
| CN106277414A (en) * | 2015-05-18 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of oil-polluted water eliminates the method for foam |
| CN106277414B (en) * | 2015-05-18 | 2018-08-14 | 中国石油化工股份有限公司 | A kind of method that oily wastewater eliminates foam |
| CN108620137A (en) * | 2017-03-15 | 2018-10-09 | 成都汇嘉春天科技有限公司 | The preparation process of organic compound depickling catalyst |
| 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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Application publication date: 20090325 |