CN101760230A - Method for catalytically deacidifying acid-containing oil - Google Patents
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- CN101760230A CN101760230A CN 200810246530 CN200810246530A CN101760230A CN 101760230 A CN101760230 A CN 101760230A CN 200810246530 CN200810246530 CN 200810246530 CN 200810246530 A CN200810246530 A CN 200810246530A CN 101760230 A CN101760230 A CN 101760230A
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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 that removes crude oil and the acid of distillate 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 tooling cost, and causes the acid number height of petroleum products, influences the use of oil product.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.Common acid number is an acid-containing raw oil greater than the crude oil of 0.5mgKOH/g, and acid number is a high-acid crude oil greater than the crude oil of 1.0mgKOH/g.
Acid in the 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%, mainly is to be caused by naphthenic acid to the corrosion of processing units.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, shortening depickling method, hot depickling, catalyse pyrolysis depickling method etc.The catalyse pyrolysis depickling is to add catalyzer in oil product, promotes the petroleum acid decarboxylation, can under lower temperature of reaction, react, and the acid removal rate height.
Disclose among the CN1272869A under the condition that does not have hydrogen to exist, at 204～426 ℃, normal atmosphere 15～1000psi keeps water and CO with the catalyzer 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.
Disclosing among the US2006016723A1 combines with alkaline earth metal oxide, transition metal oxide and clay absorbents such as rare-earth oxide and kaolin carries out catalytic decarboxylation reaction to crude oil, temperature of reaction is 200～450 ℃, and reactive system can be sealed glass tube, autoclave, flow reactor, batch reactor, slurry-phase reactor and their combination etc.
CN 1903991A has announced a kind of catalytic deacidification method of hydrocarbon raw material, comprise described hydrocarbon feed 100～300 ℃ 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 the active reduction of the existing hot acid stripping method catalyst system therefor of catalysis depickling is very fast, and catalyst life is all relatively short.
Summary of the invention
The problem to be solved in the present invention is to contain the active reduction of sour oily deacidifying catalyst in the prior art soon, and the life-span is short, and a kind of catalyst activity height, long method for catalytically deacidifying acid-containing oil of life-span are provided.
Method for catalytically deacidifying acid-containing oil provided by the invention is introduced reactor with the acid-containing hydrocarbon oil raw material, contacts with protective material, removes the carbon residue precursor in the stock oil, contacts with the catalytic deacidification catalyzer then to carry out the hydrocarbon ils that the depickling reaction obtains the acid number reduction; Described protective material bed temperature is 200～380 ℃, and described reaction bed temperature is 200～380 ℃, and the merging dividing potential drop of water and carbonic acid gas is not more than 350kPa in the reactor, weight hourly space velocity is 0.1～50hr
-1
In the method provided by the invention, described protective material is selected from one or more in aluminum oxide, rectorite leng, polynite, natural diatomaceous earth and the alumino silica gel.Preferred protectant mean pore size is 80～
Specific surface area is 120～400m
2/ g, pore volume are 0.40～1.0cm
3/ g.
In the 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 be prepared into loaded catalyst, also can be prepared into composite catalyst through mechanically mixing.In the gross weight of catalyzer, contain the alkaline earth metal oxide of 0.1～100wt%, the transition metal oxide of 0～50wt% and the carrier of 0～99.9wt% in the described deacidifying catalyst.
Preferred scheme of described catalytic deacidification catalyzer is that the employing metal oxide component loads on the loaded catalyst on the carrier, catalyzer is made up of alkaline earth metal oxide and carrier, contain or do not contain transition metal oxide, in the gross weight of catalyzer, described catalytic deacidification catalyzer contains the alkaline earth metal oxide of 0.1～20wt%, the transition metal oxide of 0～8wt% and the carrier of 80～99.9wt%.
Another preferred scheme of described catalytic deacidification catalyzer is to adopt mixed catalyst, in the gross weight of catalyzer, contains the alkaline earth metal oxide of 60～100wt%, the transition metal oxide of 0～40wt% in the 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, the 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～
In the method provided by the invention, the temperature of described beds is preferably 300～350 ℃, and the merging dividing potential drop of described water and carbonic acid gas preferably is no more than 200kPa, more preferably no more than 100kPa.
In the 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:
Because contain the carbon residue precursor that is easy to green coke in a large number in acid-containing raw oil and the distillate, this type of material molecule is big, complex structure, saturation ratio is low, and the aromaticity height is easy to be deposited on obstruction duct in the duct of deacidifying catalyst, makes catalyst deactivation.Provided by the inventionly contain sour oily acid stripping method; wide-aperture protective material is set before deacidifying catalyst; protective material can hold more carbon residue precursor, has reduced the absorption of this part material on deacidifying catalyst, makes deacidifying catalyst have higher depickling activity and stable.
Embodiment
To be described further effect of the present invention by embodiment below, but therefore not limit the present invention.
Comparative Examples 1
Adopt the deacidification effect of deacidifying catalyst in the Comparative Examples 1 explanation prior art separately.
(1) preparation deacidifying catalyst nano magnesia of the prior art:
According to the method in the document " the synthetic and sign of novel bitter earth nano band coprecipitation method " (Chinese Journal of Inorganic Chemistry, 2005,21 (6)), get 56g (NH
4)
2CO
3Be dissolved in the 1200mL deionized water, be heated to 70 ℃, measure 80mL ammoniacal liquor, add (NH
4)
2CO
3Form mixed precipitant in the solution; Get 64 gram Mg (NO
3)
26H
2O is dissolved in the 1200mL deionized water, under stirring state, the mixed precipitant that is warming up to 70 ℃ is quickly poured in the magnesium nitrate solution; Stop after 40 minutes stirring, the about 30min of ageing at room temperature filters, washs 80 ℃ of constant pressure and dries of filter cake, in 500～700 ℃ of calcinings, obtain the 10g nano magnesia, then through compression molding, be broken into 20～40 orders, be designated as C-1, composition and pore structure data see Table 1.
(2) acid-containing raw oil depickling experiment
Use the continuously feeding fixed-bed micro-reactor to estimate the acid-containing raw oil deacidification effect, filling 10g catalyzer C-1 in the reactor, feeding acid number is the distillate 1 of 7.5mgKOH/g, and stock oil character sees Table 2, and temperature of reaction is 350 ℃, and weight hourly space velocity is 1.0hr
-1, keep water and CO with nitrogen purging
2The merging dividing potential drop be 100kPa.The oil-feed analysis acid number that draws oil sample after 1.0 hours, and calculate acid removal rate, with this initial activity as 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 an acid removal rate 83.0%, and depickling the results are shown in Table 3.
Annotate: the TAN of acid removal rate=(TAN of oil sample is collected in the TAN-reaction back of raw material) * 100/ raw material.
Embodiment 1
The deacidification effect of embodiment 1 explanation method provided by the invention.
(1) preparation protective material
Pseudo-boehmite and binding agent by mixing the back extruded moulding at 2: 1, after drying, the 550 ℃ of roastings, are broken into 20～40 orders, are designated as P-1, form and the pore structure data see Table 1.
(2) the protectant acid-containing raw oil depickling experiment of filling
Adopt the evaluating apparatus in the Comparative Examples 1, reactor loads 10g protective material P-1 at the middle and upper levels, the filling 10g of lower floor deacidifying catalyst C-1; raw material is that acid number is the distillate 1 of 7.5mgKOH/g; stock oil character sees Table 2, and the protective material bed temperature is 250 ℃, and weight hourly space velocity is 1.0hr
-1, the deacidifying catalyst bed temperature is 350 ℃, weight hourly space velocity is 1.0hr
-1, keep water and CO with nitrogen purging
2The merging dividing potential drop be 100kPa.Calculate catalyzer initial activity and stabilizing active according to the method in the Comparative Examples 1, initial activity is an acid removal rate 98.2%, and depickling the results are shown in Table 3.
Embodiment 2
The deacidification effect of embodiment 2 explanations method provided by the invention.
(1) preparation protective material
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 the high sodium aluminate solution of 54mL (Chang Ling oil-refining chemical factory catalyst plant product, proportion 1.33, Al
2O
3Content 41g/L, Na
2O content 297g/L), after mixing,, get its 220g then, 215ml alum liquor (Chang Ling oil-refining chemical factory catalyst plant product, proportion 1.28, Al in aged at room temperature 24 hours
2O
3Content 102g/L, Na
2O content 155.1g/L) and the 280ml deionized water, be added in 6401 water glass, add the back and continued violent stirring 1 hour, then with gel 60 ℃ aging 20 hours.Behind the preparation alumino silica gel, be broken into 20～40 orders, be designated as P-2, composition and pore structure data see Table 1.
(2) the acid-containing raw oil catalyst depickling experiment of filling protective material P-2
Adopt reaction unit and evaluation method among the embodiment 1 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; the filling deacidifying catalyst 10g C-1 of lower floor; raw material is that acid number is the distillate 1 of 7.5mgKOH/g; stock oil character sees Table 2; the protective material bed temperature is 250 ℃, and weight hourly space velocity is 40.0hr
-1, the deacidifying catalyst bed temperature is 350 ℃, weight hourly space velocity is 40hr
-1, keep water and CO with nitrogen purging
2The merging dividing potential drop be 180kPa.Calculate catalyzer initial activity and stabilizing active according to the method in the Comparative Examples 1, depickling the results are shown in Table 3.Initial activity is an acid removal rate 97.6%.
Comparative Examples 2
Adopt the deacidification effect of deacidifying catalyst calcium oxide/chromic oxide in the Comparative Examples 2 explanation prior aries separately.
(1) preparation deacidifying catalyst
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 see Table 1.
(2) acid-containing raw oil catalytic deacidification experiment
Adopt the fixed-bed micro-reactor of the continuously feeding in the Comparative Examples 1 to carry out the experiment of acid-containing raw oil catalytic deacidification, filling 10g deacidifying catalyst C-2 in the reactor, raw materials used is that acid number is the distillate 2 of 4.6mgKOH/g, stock oil character sees Table 2, temperature of reaction is 300 ℃, and weight hourly space velocity is 5.0hr
-1, keep water and CO with nitrogen purging
2The merging dividing potential drop be 150kPa.Calculate catalyzer initial activity and stabilizing active according to the method in the Comparative Examples 1, depickling the results are shown in Table 3.
Embodiment 3
The deacidification effect of embodiment 3 explanations method provided by the invention.
Used evaluating apparatus is identical with embodiment 1 with method, and reactor loads 10g protective material P-2 at the middle and upper levels, the filling deacidifying catalyst 10g C-2 of lower floor; raw material is that acid number is the distillate 2 of 4.6mgKOH/g; stock oil character sees Table 2, and the protective material bed temperature is 300 ℃, and weight hourly space velocity is 10.0hr
-1, the deacidifying catalyst bed temperature is 300 ℃, weight hourly space velocity is 10.0hr
-1, keep water and CO with nitrogen purging
2The merging dividing potential drop be 150kPa.Calculate catalyzer initial activity and stabilizing active according to the method in the Comparative Examples 1, the initial activity of combination catalyst is an acid removal rate 95.7%, and depickling the results are shown in Table 3.
Comparative Examples 3
Adopt the deacidification effect of deacidifying catalyst magnesium oxide/aluminum oxide in the Comparative Examples 3 explanation prior aries separately.
(1) preparation deacidifying catalyst
The P-1 of pseudo-boehmite and adhesive preparation with saturated pickling process load thereon 16% (in vehicle weight) magnesium oxide, is designated as MA-1, forms and the pore structure data see Table 1.
(2) contain the experiment of acid fraction oil catalytic deacidification
Reaction unit and evaluation method are loaded 10g catalyzer MA-1 with Comparative Examples 1 in the reactor, raw material is that acid number is the distillate 3 of 10.2mgKOH/g, and stock oil character sees Table 2, and temperature of reaction is 250 ℃, and weight hourly space velocity is 40.0hr
-1, keep water and CO with nitrogen purging
2The merging dividing potential drop be 200kPa.Calculate catalyzer initial activity and stabilizing active according to the method in the Comparative Examples 1, the initial activity of MA-1 catalyzer is an acid removal rate 81.7%, and depickling the results are shown in Table 4.
Embodiment 4
The deacidification effect of embodiment 4 explanations method provided by the invention.
Adopt reaction unit and evaluation method in the Comparative Examples 1, reactor loads 10g protective material P-1 at the middle and upper levels, the filling depickling 10g of lower floor catalyzer MA-1; raw material is that acid number is the distillate 3 of 10.2mgKOH/g; stock oil character sees Table 2, and the protective material bed temperature is 350 ℃, and weight hourly space velocity is 20.0hr
-1, the deacidifying catalyst bed temperature is 250 ℃, weight hourly space velocity is 20.0hr
-1, keep water and CO with nitrogen purging
2The merging dividing potential drop be 200kPa.Calculate catalyzer initial activity and stabilizing active according to the method in the Comparative Examples 1, the initial activity of combination catalyst is an acid removal rate 99.1%, and depickling the results are shown in Table 4.
Comparative Examples 4
Adopt the deacidification effect of deacidifying catalyst calcium oxide/silicon oxide in the Comparative Examples 3 explanation prior aries separately.
(1) preparation deacidifying catalyst
With the silicon oxide is carrier, and the silver suboxide with the calcium oxide and 2.1% (in vehicle weight) of saturated pickling process load thereon 8.5% (in vehicle weight) is designated as MA-2, forms and the pore structure data see Table 1.
(2) contain the experiment of acid fraction oil catalytic deacidification
Adopt reaction unit and evaluation method in the Comparative Examples 1, filling 10g catalyzer MA-2 in the reactor, raw materials used is that acid number is the dewatering and desalting crude oil A of 5.3mgKOH/g, and stock oil character sees Table 2, and temperature of reaction is 350 ℃, and weight hourly space velocity is 20.0hr
-1, keep water and CO with nitrogen purging
2The merging dividing potential drop be 300kPa.Calculate catalyzer initial activity and stabilizing active according to the method in the Comparative Examples 1, the initial activity of MA-2 catalyzer is an acid removal rate 69.0%, and depickling the results are shown in Table 4.
Embodiment 5
The deacidification effect of embodiment 5 explanations acid-containing raw oil acid stripping method provided by the invention.
Adopt reaction unit and evaluation method in the Comparative Examples 1; reactor loads 10g protective material P-2 at the middle and upper levels; the filling depickling 10g of lower floor catalyzer MA-2; raw materials used is that acid number is the desalted and dewatered crude oil A of 5.3mgKOH/g; stock oil character sees Table 2; the protective material bed temperature is 300 ℃, and weight hourly space velocity is 30.0hr
-1, the deacidifying catalyst bed temperature is 350 ℃, weight hourly space velocity is 30hr
-1, keep water and CO with nitrogen purging
2The merging dividing potential drop be 300kPa, calculate catalyzer initial activity and stabilizing active according to the method in the Comparative Examples 1, the initial activity of combination catalyst is an acid removal rate 96.2%, depickling the results are shown in Table 4.
Table 1 catalyzer and protective material are formed and rerum natura
Table 2 stock oil character
| The stock oil numbering | Distillate 1 | Distillate 2 | Distillate 3 | Dewatering and desalting crude oil A |
| Density (20 ℃)/(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 ℃)/(mm 2/s) | ??4.61 | ??6.501(50℃) | ??5.12 | ?- |
| Kinematic viscosity (80 ℃)/(mm 2/s) | ??- | ??- | ??- | ?20.38 |
| The stock oil numbering | Distillate 1 | Distillate 2 | Distillate 3 | Dewatering and desalting crude oil A |
| Boiling range, wt% 0-200 ℃ 200-350 ℃＞350 ℃ | ??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
| The embodiment numbering | Comparative Examples 1 | Embodiment 1 | Embodiment 2 | Comparative Examples 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, ℃ 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, the % 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
| The embodiment numbering | Comparative Examples 3 | Embodiment 4 | Comparative Examples 4 | Embodiment 5 |
| Catalyst loading | ??MA-1 | ??P-1/MA-1 | ??MA-2 | ??P-2/MA-2 |
| The embodiment numbering | Comparative Examples 3 | Embodiment 4 | Comparative Examples 4 | Embodiment 5 |
| Raw material | Distillate 3 | Distillate 3 | Dewatering and desalting crude oil A | Dewatering and desalting crude oil A |
| Temperature of reaction, ℃ 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, the % initial activity | ??81.7 | ??99.1 | ??69.0 | ??96.2 |
| Stabilizing active | ??12.6 | ??46.4 | ??35.2 | ??68.9 |
By table 3 as seen, embodiment 1,2 has loaded protective material bed P-1, P-2 respectively on reactor deacidifying catalyst bed, compare with the method for 1 filling of Comparative Examples deacidifying catalyst bed, employing is with a kind of deacidifying catalyst, the acid removal rate first alive of handling same raw material has improved 14.6～15.2 percentage points, and the stabilizing active acid removal rate has improved 57.3～61.3 percentage points; Embodiment 3 has loaded protective material P-2 on the deacidifying catalyst bed, compare with Comparative Examples 2, and the acid removal rate of just living has improved 20.5 percentage points, and the stabilizing active acid removal rate has improved 63.7 percentage points; Embodiment 4 has loaded protective material P-1 on deacidifying catalyst MA-1 upper strata, compares with Comparative Examples 3, and the acid removal rate of just living has improved 17.4 percentage points, and the stabilizing active acid removal rate has improved 35.8 percentage points; Embodiment 5 has loaded protective material P-2 on catalyzer deacidifying catalyst MA-2 upper strata, compares with Comparative Examples 4, and the acid removal rate of just living has improved 27.2 percentage points, and the stabilizing active acid removal rate has improved 33.7 percentage points; As seen, adopt method provided by the invention to handle the acid-containing hydrocarbon oil raw material, compare with the method that directly adopts deacidifying catalyst to handle the acid-containing hydrocarbon oil raw material in the prior art, acid removal rate has all had significant raising, particularly carry out with the reaction times, acid removal rate descends slowly, thereby has prolonged the work-ing life of deacidifying catalyst.
Claims (13)
1. a method for catalytically deacidifying acid-containing oil comprises the acid-containing hydrocarbon oil raw material is introduced reactor, contacts with protective material earlier, removes the carbon residue precursor in the stock oil, contacts with the catalytic deacidification catalyzer then to carry out the hydrocarbon ils that the depickling reaction obtains the acid number reduction; Described protective material bed temperature is 200～380 ℃, and described reaction bed temperature is 200～380 ℃, and the merging dividing potential drop of water and carbonic acid gas is not more than 350kPa in the reactor, weight hourly space velocity is 0.1～50hr
-1
2. according to the method for claim 1, it is characterized in that described protective material is selected from one or more in aluminum oxide, rectorite leng, polynite, natural diatomaceous earth and the 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 are 0.40～1.0cm
3/ g.
4. according to the method for claim 1, it is characterized in that described catalytic deacidification catalyzer contains alkaline earth metal oxide, contain or do not contain transition metal oxide, contain or do not contain carrier.
5. according to the method for claim 4, it is characterized in that in the described catalytic deacidification catalyzer, in the gross weight of catalyzer, contain the alkaline earth metal oxide of 0.1～100wt%, the transition metal oxide of 0～50wt% and the carrier of 0～99.9wt% in the described deacidifying catalyst.
6. according to the method for claim 5, it is characterized in that containing in the described catalytic deacidification catalyzer alkaline earth metal oxide of 0.1～20wt%, the transition metal oxide of 0～8wt% and the carrier of 80.0～99.9wt%.
7. according to the method for claim 5, it is characterized in that containing in the described catalytic deacidification catalyzer alkaline earth metal oxide of 60～100wt%, the transition metal oxide of 0～40wt%.
8. according to a kind of method in the claim 4,5,6 and 7, it is characterized in that described alkaline earth metal oxide is MgO and/or CaO.
9. according to the method for claim 8, it is characterized in that described alkaline earth metal oxide is a nano magnesia.
10. according to a kind of method in the claim 4,5,6 and 7, it is characterized in that described transition metal is selected from one or more in Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, Zn and the rare earth metal.
11. the method according to claim 1 is characterized in that, described reaction bed temperature is 300～350 ℃, and the merging dividing potential drop of described water and carbonic acid gas is no more than 200kPa.
12., it 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 according to the method for claim 1.
13., it 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 according to the method for claim 12.
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| CN104492412A (en) * | 2015-01-07 | 2015-04-08 | 李�杰 | Preparation method of petroleum deacidification catalyst |
| 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 |
| CN113388417A (en) * | 2020-03-13 | 2021-09-14 | 中石化南京化工研究院有限公司 | Heat-conducting oil online alkaline protective agent and preparation method and application thereof |
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| US5688741A (en) * | 1995-03-17 | 1997-11-18 | Intevep, S.A. | Process and catalyst for upgrading heavy hydrocarbon |
| CN101240189B (en) * | 2007-02-09 | 2011-06-22 | 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104492412A (en) * | 2015-01-07 | 2015-04-08 | 李�杰 | Preparation method of petroleum deacidification catalyst |
| 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 |
| CN113388417A (en) * | 2020-03-13 | 2021-09-14 | 中石化南京化工研究院有限公司 | Heat-conducting oil online alkaline protective agent and preparation method and application thereof |
| 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 |
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