CN101760230B - Method for catalytically deacidifying acid-containing oil - Google Patents
Method for catalytically deacidifying acid-containing oil Download PDFInfo
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- CN101760230B CN101760230B CN200810246530.9A CN200810246530A CN101760230B CN 101760230 B CN101760230 B CN 101760230B CN 200810246530 A CN200810246530 A CN 200810246530A CN 101760230 B CN101760230 B CN 101760230B
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Abstract
The invention relates to a method for catalytically deacidifying acid-containing oil, which includes the following steps that: acid-containing raw hydrocarbon oil is led into a reactor, and is first contacted with protective agent, so that the residual carbon precursor in the raw oil can be removed, and the oil is then contacted with catalytic deacidification catalyst, so that deacidification reaction occurs to produce hydrocarbon oil with a reduced acid value; the protective agent bed temperature is 200 DEG C to 380 DEG C, the catalyst bed temperature is 200 DEG C to 380 DEG C, the combined partial pressure of water and carbon dioxide in the reactor is not larger than 350kPa, and the weight hourly space velocity is 0.1hr-1 to 50hr-1. The method arranges the large-aperture protective agent before the deacidification catalyst, the protective agent can contain a large amount of residual carbon precursor, so that less residual carbon precursor can be absorbed on the deacidification catalyst, and thereby the deacidification catalyst, has high deacidification activity and stability.
Description
Technical field
The present invention relates to a kind of method removing crude oil and the acid of distillate PetroChina Company Limited..
Background technology
Along with the day by day exhausted of petroleum resources and oil recovery technique improve constantly, crude oil production scope constantly expands, 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, affects the long period safe handling of oil refining apparatus, increases tooling cost, and causes the acid number of petroleum products high, affect the use of oil product.Acid number (TAN) be in and the total amount of KOH that in 1g crude oil, various acidic components consume, represent (see ASTMD-664 method) with mgKOH/g.The crude oil that common acid number is greater than 0.5mgKOH/g is acid-containing raw oil, and the crude oil that acid number is greater than 1.0mgKOH/g is high-acid crude oil.
Acid in crude oil comprises naphthenic acid, lipid acid, aromatic acid, mineral acid, mercaptan, hydrogen sulfide and phenol etc., and wherein the content of naphthenic acid accounts for 90%, is mainly caused by naphthenic acid the corrosion of processing units.At present, the production technology of acid-containing raw oil and distillate Naphthenic Acid Removal mainly comprises: chemical extraction method, adsorption method of separation, solvent extraction process, esterification deacidification method, shortening depickling method, hot depickling, catalyse pyrolysis depickling method etc.Catalyse pyrolysis depickling adds catalyzer in oil product, promotes petroleum acid decarboxylation, can react, and acid removal rate is high under lower temperature of reaction.
Disclose in CN1272869A and do not having under hydrogen existent condition, with the oil soluble of VB, VIB, VIIB, group VIII metal or the catalyzer of oil-dispersing property metallic compound at 204 ~ 426 DEG C, normal atmosphere 15 ~ 1000psi, maintains water and CO
2merge dividing potential drop, lower than under the condition of 50psi, catalytic decarboxylation is carried out to crude oil or distillate.
Disclosing in US2006016723A1 combines with alkaline earth metal oxide, transition metal oxide and the clay absorbent such as rare-earth oxide and kaolin carries out catalytic decarboxylation reaction to crude oil, temperature of reaction is 200 ~ 450 DEG C, and reactive system can be sealed glass tube, autoclave, flow reactor, batch reactor, slurry-phase reactor and their combination etc.
CN 1903991A discloses a kind of catalytic deacidification method of hydrocarbon raw material, comprise described hydrocarbon feed 100 ~ 300 DEG C and deacidifying catalyst contact reacts, 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.
But existing catalytic thermal acid stripping method used catalyst depickling activity reduces very fast, and catalyst life is all relatively short.
Summary of the invention
The problem to be solved in the present invention reduces fast containing sour oily deacidifying catalyst activity in prior art, and the life-span is short, provides the method for catalytically deacidifying acid-containing oil that a kind of catalyst activity is high, the life-span is long.
Method for catalytically deacidifying acid-containing oil provided by the invention, introduces reactor by acid-containing hydrocarbon oil raw material, contacts, remove the carbon residue precursor in stock oil with protective material, then carries out depickling with catalytic deacidification catalyst exposure and is obtained by reacting the hydrocarbon ils that acid number reduces; Described protective material bed temperature is 200 ~ 380 DEG C, and described reaction bed temperature is 200 ~ 380 DEG C, and in reactor, the merging dividing potential drop of water and carbonic acid gas is not more than 350kPa, weight hourly space velocity is 0.1 ~ 50hr
-1.
In method provided by the invention, described protective material is selected from one or more in aluminum oxide, rectorite leng, polynite, natural diatomaceous earth and alumino silica gel.Preferred protectant mean pore size is 80 ~ 300
specific surface area is 120 ~ 400m
2/ g, pore volume is 0.40 ~ 1.0cm
3/ g.
In method provided by the invention, described catalytic deacidification catalyzer contains alkaline earth metal oxide, contain or do not contain transition metal oxide, contain or do not contain carrier, when described catalytic deacidification catalyzer contains carrier, can loaded catalyst be prepared into, also can be prepared into composite catalyst through mechanically mixing.With the total weight of catalyzer, the carrier containing the alkaline earth metal oxide of 0.1 ~ 100wt%, the transition metal oxide of 0 ~ 50wt% and 0 ~ 99.9wt% in described deacidifying catalyst.
Described catalytic deacidification catalyzer preferred scheme adopts the loaded catalyst of metal oxide component load on carrier, catalyzer is made up of alkaline earth metal oxide and carrier, contain or do not contain transition metal oxide, with the total weight of catalyzer, described catalytic deacidification catalyzer contains the carrier of the alkaline earth metal oxide of 0.1 ~ 20wt%, the transition metal oxide of 0 ~ 8wt% and 80 ~ 99.9wt%.
Another preferred scheme of described catalytic deacidification catalyzer adopts mixed catalyst, with the total weight of catalyzer, containing the alkaline earth metal oxide of 60 ~ 100wt%, the transition metal oxide of 0 ~ 40wt% in described catalytic deacidification catalyzer.
Described alkaline earth metal oxide is preferably MgO and/or CaO, more preferably nano magnesia; Described transition metal is one or more in Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, Zn, rare earth metal, and described carrier is aluminum oxide, silicon oxide, zirconium white.It is 50 ~ 200m that the physico-chemical property of described catalytic deacidification catalyzer is preferably specific surface area
2/ g, mean pore size is 50 ~ 300
In method provided by the invention, the temperature of described beds is preferably 300 ~ 350 DEG C, the merging dividing potential drop of described water and carbonic acid gas preferably more than 200kPa, more preferably no more than 100kPa.
In method provided by the invention, described acid-containing hydrocarbon oil raw material is crude oil and/or the distillate that acid number is not less than 0.5mgKOH/g, and more preferably acid number is not less than crude oil and/or the distillate of 1.5mgKOH/g.
The beneficial effect of method provided by the invention is:
Due in acid-containing raw oil and distillate containing the carbon residue precursor being easy to green coke in a large number, this type of material molecule is large, complex structure, and saturation ratio is low, and aromaticity is high, blocks duct, make catalyst deactivation in the duct being easy to be deposited on deacidifying catalyst.Provided by the invention containing sour oily acid stripping method; wide-aperture protective material is set before deacidifying catalyst; protective material can hold more carbon residue precursor, decreases the absorption of this part material on deacidifying catalyst, makes deacidifying catalyst have higher depickling activity and stability.
Embodiment
To be described further effect of the present invention by embodiment below, but not thereby limit the invention.
Comparative example 1
Comparative example 1 illustrates the deacidification effect adopting separately deacidifying catalyst in prior art.
(1) deacidifying catalyst nano magnesia of the prior art is prepared:
According to the method in document " New-type MgO Nanobelts via Co-precipitation Synthetic Way syntheses and properties " (Chinese Journal of Inorganic Chemistry, 2005,21 (6)), get 56g (NH
4)
2cO
3be dissolved in 1200mL deionized water, be heated to 70 DEG C, measure 80mL ammoniacal liquor, add (NH
4)
2cO
3mixed precipitant is formed in solution; Get 64 grams of Mg (NO
3)
26H
2o is dissolved in 1200mL deionized water, under agitation, is quickly poured in magnesium nitrate solution by the mixed precipitant being warming up to 70 DEG C; Stop after 40 minutes stirring, at room temperature ageing is about 30min, filters, washs, filter cake 80 DEG C of constant pressure and dries, then in 500 ~ 700 DEG C of calcinings, 10g nano magnesia is obtained, through compression molding, be broken into 20 ~ 40 orders, be designated as C-1, composition and pore structure data are in table 1.
(2) Removing Naphthenic Acid from Crude Oil experiment
Use continuously feeding fixed-bed micro-reactor to evaluate Removing Naphthenic Acid from Crude Oil effect, load 10g catalyzer C-1 in reactor, pass into the distillate 1 that acid number is 7.5mgKOH/g, stock oil character is in table 2, and temperature of reaction is 350 DEG C, and weight hourly space velocity is 1.0hr
-1, maintain water and CO with nitrogen purging
2merging dividing potential drop be 100kPa.Oil-feed is drawn oil sample after 1.0 hours analysis acid number, and calculates acid removal rate, in this, as the initial activity of catalyzer; Its acid number of crude oil sample analysis of 19.0 ~ 20.0 hours is answered in negate, and calculates acid removal rate, as the stabilizing active of catalyzer.The initial activity of C-1 catalyzer is acid removal rate 83.0%, and depickling the results are shown in Table 3.
Note: the TAN of acid removal rate=(collecting the TAN of oil sample after the TAN-reaction of raw material) × 100/ raw material.
Embodiment 1
Embodiment 1 illustrates the deacidification effect of method provided by the invention.
(1) protective material is prepared
Extruded moulding after being mixed by 2: 1 with binding agent by pseudo-boehmite, after drying, 550 DEG C of roastings, is broken into 20 ~ 40 orders, is designated as P-1, and composition and pore structure data are in table 1.
(2) experiment of protectant Removing Naphthenic Acid from Crude Oil is loaded
Adopt the evaluating apparatus in comparative example 1, reactor loads 10g protective material P-1 at the middle and upper levels, lower floor filling 10g deacidifying catalyst C-1; the distillate 1 of raw material to be acid number be 7.5mgKOH/g; stock oil character is in table 2, and protective material bed temperature is 250 DEG C, and weight hourly space velocity is 1.0hr
-1, deacidifying catalyst bed temperature is 350 DEG C, and weight hourly space velocity is 1.0hr
-1, maintain water and CO with nitrogen purging
2merging dividing potential drop be 100kPa.Calculate catalyzer initial activity and stabilizing active according to the method in comparative example 1, initial activity is acid removal rate 98.2%, and depickling the results are shown in Table 3.
Embodiment 2
Embodiment 2 illustrates the deacidification effect of method provided by the invention.
(1) protective material is prepared
Get 100ml water glass (Chang Ling oil-refining chemical factory catalyst plant product, proportion 1.26, SiO
2content 250g/L, modulus 3.25) put into a beaker, add 54mL height sodium aluminate solution (Chang Ling oil-refining chemical factory catalyst plant product, proportion 1.33, Al
2o
3content 41g/L, Na
2o content 297g/L), after mixing, in aged at room temperature 24 hours, then get its 220g, 215ml alum liquor (Chang Ling oil-refining chemical factory catalyst plant product, proportion 1.28, Al
2o
3content 102g/L, Na
2o content 155.1g/L) and 280ml deionized water, be added in 6401 water glass, add rear continuation violent stirring 1 hour, then that gel is aging 20 hours at 60 DEG C.After preparing alumino silica gel, be broken into 20 ~ 40 orders, be designated as P-2, composition and pore structure data are in table 1.
(2) the acid-containing raw oil catalyst depickling experiment of protective material P-2 is loaded
The reaction unit in embodiment 1 and evaluation method is adopted to carry out the experiment of acid-containing raw oil catalytic deacidification; reactor loads 10g protective material P-2 at the middle and upper levels; lower floor filling deacidifying catalyst 10g C-1; the distillate 1 of raw material to be acid number be 7.5mgKOH/g; stock oil character is in table 2; protective material bed temperature is 250 DEG C, and weight hourly space velocity is 40.0hr
-1, deacidifying catalyst bed temperature is 350 DEG C, and weight hourly space velocity is 40hr
-1, maintain water and CO with nitrogen purging
2merging dividing potential drop be 180kPa.Calculate catalyzer initial activity and stabilizing active according to the method in comparative example 1, depickling the results are shown in Table 3.Initial activity is acid removal rate 97.6%.
Comparative example 2
Comparative example 2 illustrates the deacidification effect adopting separately deacidifying catalyst calcium oxide/chromic oxide in prior art.
(1) deacidifying catalyst is prepared
Get 9.0g calcium oxide and 1.0g chromic oxide, mechanically mixing is even, and compression molding, is broken into 20 ~ 40 orders, is designated as C-2, and composition and pore structure data are in table 1.
(2) acid-containing raw oil catalytic deacidification experiment
The fixed-bed micro-reactor of the continuously feeding in comparative example 1 is adopted to carry out the experiment of acid-containing raw oil catalytic deacidification, 10g deacidifying catalyst C-2 is loaded in reactor, the distillate 2 of raw materials used to be acid number be 4.6mgKOH/g, stock oil character is in table 2, temperature of reaction is 300 DEG C, and weight hourly space velocity is 5.0hr
-1, maintain water and CO with nitrogen purging
2merging dividing potential drop be 150kPa.Calculate catalyzer initial activity and stabilizing active according to the method in comparative example 1, depickling the results are shown in Table 3.
Embodiment 3
Embodiment 3 illustrates the deacidification effect of method provided by the invention.
Evaluating apparatus used is identical with embodiment 1 with method, and reactor loads 10g protective material P-2 at the middle and upper levels, lower floor filling deacidifying catalyst 10g C-2; the distillate 2 of raw material to be acid number be 4.6mgKOH/g; stock oil character is in table 2, and protective material bed temperature is 300 DEG C, and weight hourly space velocity is 10.0hr
-1, deacidifying catalyst bed temperature is 300 DEG C, and weight hourly space velocity is 10.0hr
-1, maintain water and CO with nitrogen purging
2merging dividing potential drop be 150kPa.Calculate catalyzer initial activity and stabilizing active according to the method in comparative example 1, the initial activity of combination catalyst is acid removal rate 95.7%, and depickling the results are shown in Table 3.
Comparative example 3
Comparative example 3 illustrates the deacidification effect adopting separately deacidifying catalyst magnesium oxide/aluminum oxide in prior art.
(1) deacidifying catalyst is prepared
P-1 pseudo-boehmite and binding agent prepared saturated pickling process load thereon 16% (in vehicle weight) magnesium oxide, is designated as MA-1, and composition and pore structure data are in table 1.
(2) containing the experiment of acid fraction oil catalytic deacidification
Reaction unit and evaluation method, with comparative example 1, load 10g catalyzer MA-1 in reactor, the distillate 3 of raw material to be acid number be 10.2mgKOH/g, stock oil character is in table 2, and temperature of reaction is 250 DEG C, and weight hourly space velocity is 40.0hr
-1, maintain water and CO with nitrogen purging
2merging dividing potential drop be 200kPa.Calculate catalyzer initial activity and stabilizing active according to the method in comparative example 1, the initial activity of MA-1 catalyzer is acid removal rate 81.7%, and depickling the results are shown in Table 4.
Embodiment 4
Embodiment 4 illustrates the deacidification effect of method provided by the invention.
Adopt the reaction unit in comparative example 1 and evaluation method, reactor loads 10g protective material P-1 at the middle and upper levels, lower floor filling depickling 10g catalyzer MA-1; the distillate 3 of raw material to be acid number be 10.2mgKOH/g; stock oil character is in table 2, and protective material bed temperature is 350 DEG C, and weight hourly space velocity is 20.0hr
-1, deacidifying catalyst bed temperature is 250 DEG C, and weight hourly space velocity is 20.0hr
-1, maintain water and CO with nitrogen purging
2merging dividing potential drop be 200kPa.Calculate catalyzer initial activity and stabilizing active according to the method in comparative example 1, the initial activity of combination catalyst is acid removal rate 99.1%, and depickling the results are shown in Table 4.
Comparative example 4
Comparative example 3 illustrates the deacidification effect adopting separately deacidifying catalyst calcium oxide/silicon oxide in prior art.
(1) deacidifying catalyst is prepared
Take silicon oxide as carrier, with the silver suboxide of the calcium oxide and 2.1% (in vehicle weight) of saturated pickling process load thereon 8.5% (in vehicle weight), be designated as MA-2, composition and pore structure data are in table 1.
(2) containing the experiment of acid fraction oil catalytic deacidification
Adopt the reaction unit in comparative example 1 and evaluation method, load 10g catalyzer MA-2 in reactor, the dewatering and desalting crude oil A of raw materials used to be acid number be 5.3mgKOH/g, stock oil character is in table 2, and temperature of reaction is 350 DEG C, and weight hourly space velocity is 20.0hr
-1, maintain water and CO with nitrogen purging
2merging dividing potential drop be 300kPa.Calculate catalyzer initial activity and stabilizing active according to the method in comparative example 1, the initial activity of MA-2 catalyzer is acid removal rate 69.0%, and depickling the results are shown in Table 4.
Embodiment 5
Embodiment 5 illustrates the deacidification effect of Removing Naphthenic Acid from Crude Oil method provided by the invention.
Adopt the reaction unit in comparative example 1 and evaluation method; reactor loads 10g protective material P-2 at the middle and upper levels; lower floor filling depickling 10g catalyzer MA-2; the desalted and dewatered crude oil A of raw materials used to be acid number be 5.3mgKOH/g; stock oil character is in table 2; protective material bed temperature is 300 DEG C, and weight hourly space velocity is 30.0hr
-1, deacidifying catalyst bed temperature is 350 DEG C, and weight hourly space velocity is 30hr
-1, maintain water and CO with nitrogen purging
2merging dividing potential drop be 300kPa, calculate catalyzer initial activity and stabilizing active according to the method in comparative example 1, the initial activity of combination catalyst is acid removal rate 96.2%, and depickling the results are shown in Table 4.
Table 1 catalyzer and protective material form and physical property
Table 2 stock oil character
| Stock oil is numbered | Distillate 1 | Distillate 2 | Distillate 3 | Dewatering and desalting crude oil A |
| Density (20 DEG C)/(g/cm 3) | 0.8090 | 0.8450 | 0.8325 | 0.9224 |
| Carbon residue/% | 0.13 | 0.01 | 0.20 | 5.67 |
| Acid number/mgKOH/g | 7.5 | 4.6 | 10.2 | 5.3 |
| Kinematic viscosity (20 DEG C)/(mm 2/s) | 4.61 | 6.501(50℃) | 5.12 | - |
| Kinematic viscosity (80 DEG C)/(mm 2/s) | - | - | - | 20.38 |
| Boiling range, wt% 0-200 DEG C 200-350 DEG C > 350 DEG C | 8.70 86.30 5.00 | 0.0 39.2 60.8 | 9.81 87.39 2.80 | 7.21 22.10 70.69 |
Table 3
| Embodiment is numbered | Comparative example 1 | Embodiment 1 | Embodiment 2 | Comparative example 2 | Embodiment 3 |
| Catalyst loading | C-1 | P-1/C-1 | P-2/C-1 | C-2 | P-2/C-2 |
| Raw material | Distillate 1 | Distillate 1 | Distillate 1 | Distillate 2 | Distillate 2 |
| Temperature of reaction, DEG C protective material bed | - | 250 | 250 | - | 300 |
| Beds | 350 | 350 | 350 | 300 | 300 |
| Weight hourly space velocity, hr -1 | 1.0 | 1.0 | 40.0 | 5.0 | 10.0 |
| H 2O+CO 2Merge dividing potential drop, kPa | 100 | 100 | 180 | 150 | 150 |
| Raw material acid number TAN | 7.5 | 7.5 | 7.5 | 4.6 | 4.6 |
| Product acid number TAN | 5.1 | 0.5 | 0.8 | 3.67 | 0.74 |
| Acid removal rate, % initial activity | 83.0 | 98.2 | 97.6 | 75.2 | 95.7 |
| Stabilizing active | 32 | 93.3 | 89.3 | 20.3 | 84.0 |
Table 4
| Embodiment is numbered | Comparative example 3 | Embodiment 4 | Comparative example 4 | Embodiment 5 |
| Catalyst loading | MA-1 | P-1/MA-1 | MA-2 | P-2/MA-2 |
| Raw material | Distillate 3 | Distillate 3 | Dewatering and desalting crude oil A | Dewatering and desalting crude oil A |
| Temperature of reaction, DEG C protective material bed | - | 350 | - | 300 |
| Beds | 250 | 250 | 350 | 350 |
| Weight hourly space velocity, hr -1 | 40.0 | 20.0 | 20.0 | 30.0 |
| H 2O+CO 2Merge dividing potential drop, kPa | 200 | 200 | 300 | 300 |
| Raw material acid number TAN | 10.2 | 10.2 | 5.3 | 5.3 |
| Stable prod acid number TAN | 8.91 | 5.47 | 3.43 | 1.65 |
| Acid removal rate, % initial activity | 81.7 | 99.1 | 69.0 | 96.2 |
| Stabilizing active | 12.6 | 46.4 | 35.2 | 68.9 |
From table 3, embodiment 1,2 has loaded protective material bed P-1, P-2 respectively on reactor deacidifying catalyst bed, compare with the method for comparative example 1 filling deacidifying catalyst bed, adopt same deacidifying catalyst, the acid removal rate first alive processing same raw material improves 14.6 ~ 15.2 percentage points, and stabilizing active acid removal rate improves 57.3 ~ 61.3 percentage points; Embodiment 3 has loaded protective material P-2 on deacidifying catalyst bed, compares with comparative example 2, and acid removal rate of just living improves 20.5 percentage points, and stabilizing active acid removal rate improves 63.7 percentage points; Embodiment 4 has loaded protective material P-1 on deacidifying catalyst MA-1 upper strata, compares with comparative example 3, and acid removal rate of just living improves 17.4 percentage points, and stabilizing active acid removal rate improves 35.8 percentage points; Embodiment 5 has loaded protective material P-2 on catalyzer deacidifying catalyst MA-2 upper strata, compares with comparative example 4, and acid removal rate of just living improves 27.2 percentage points, and stabilizing active acid removal rate improves 33.7 percentage points; Visible, adopt method process acid-containing hydrocarbon oil raw material provided by the invention, compare with directly adopting the method for deacidifying catalyst process acid-containing hydrocarbon oil raw material in prior art, acid removal rate has had significant raising, particularly carry out with the reaction times, acid removal rate declines slowly, thus extends the work-ing life of deacidifying catalyst.
Claims (12)
1. a method for catalytically deacidifying acid-containing oil, comprises and acid-containing hydrocarbon oil raw material is introduced reactor, first contacts with protective material, removes the carbon residue precursor in stock oil, then carries out depickling with catalytic deacidification catalyst exposure and is obtained by reacting the hydrocarbon ils that acid number reduces; Described protective material bed temperature is 200 ~ 380 DEG C, and described reaction bed temperature is 200 ~ 380 DEG C, and in reactor, the merging dividing potential drop of water and carbonic acid gas is not more than 350kPa, weight hourly space velocity is 0.1 ~ 50hr
-1; Described catalytic deacidification catalyzer contains alkaline earth metal oxide, contains or not containing transition metal oxide, contains or do not contain carrier.
2., according to the method for claim 1, it is characterized in that one or more that described protective material is selected from aluminum oxide, rectorite leng, polynite, natural diatomaceous earth and alumino silica gel.
3., according to the method for claim 2, it is characterized in that described protectant mean pore size is
specific surface area is 120 ~ 400m
2/ g, pore volume is 0.40 ~ 1.0cm
3/ g.
4. according to the method for claim 1, it is characterized in that in described catalytic deacidification catalyzer, with the total weight of catalyzer, the carrier containing the alkaline earth metal oxide of 0.1 ~ 100wt%, the transition metal oxide of 0 ~ 50wt% and 0 ~ 99.9wt% in described deacidifying catalyst.
5., according to the method for claim 4, it is characterized in that the carrier containing the alkaline earth metal oxide of 0.1 ~ 20wt%, the transition metal oxide of 0 ~ 8wt% and 80.0 ~ 99.9wt% in described catalytic deacidification catalyzer.
6., according to the method for claim 4, it is characterized in that in described catalytic deacidification catalyzer containing the alkaline earth metal oxide of 60 ~ 100wt%, the transition metal oxide of 0 ~ 40wt%.
7., according to any one method in claim 1,4,5 and 6, it is characterized in that described alkaline earth metal oxide is MgO and/or CaO.
8., according to the method for claim 7, it is characterized in that described alkaline earth metal oxide is nano magnesia.
9., according to any one method in claim 1,4,5 and 6, it is characterized in that one or more that described transition metal is selected from Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, Zn and rare earth metal.
10. according to the method for claim 1, it is characterized in that, described reaction bed temperature is 300 ~ 350 DEG C, and the merging dividing potential drop of described water and carbonic acid gas is no more than 200kPa.
11., according to the method for claim 1, is characterized in that described acid-containing hydrocarbon oil raw material is crude oil and/or the distillate that acid number is not less than 0.5mgKOH/g.
12., according to the method for claim 11, is characterized in that described acid-containing hydrocarbon oil raw material is crude oil and/or the distillate that acid number is not less than 1.5mgKOH/g.
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| CN113388417B (en) * | 2020-03-13 | 2023-04-18 | 中国石油化工股份有限公司 | Heat-conducting oil online alkaline protective agent and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5688395A (en) * | 1995-03-17 | 1997-11-18 | Intevep, S.A. | Process and catalyst for upgrading heavy hydrocarbon |
| CN101240189A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Fixed bed hydrogenation treatment method for acid-containing crude oil |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5688395A (en) * | 1995-03-17 | 1997-11-18 | Intevep, S.A. | Process and catalyst for upgrading heavy hydrocarbon |
| CN101240189A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Fixed bed hydrogenation treatment method for acid-containing crude oil |
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