CN101537363B - Deacidifying catalyst and preparation method and application thereof - Google Patents
Deacidifying catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN101537363B CN101537363B CN2009100647114A CN200910064711A CN101537363B CN 101537363 B CN101537363 B CN 101537363B CN 2009100647114 A CN2009100647114 A CN 2009100647114A CN 200910064711 A CN200910064711 A CN 200910064711A CN 101537363 B CN101537363 B CN 101537363B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- active component
- weight
- deacidifying
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a deacidifying catalyst and a preparation method and application thereof. The deacidifying catalyst converts and removes petroleum acid in crude oil and distillate oil thereof at relatively moderate temperature. The deacidifying catalyst consists of 80-95% of a carrier, 1-20% of an active component A and 1-20% of an active component B to total weight of the deacidifying catalyst, wherein, the carrier is one of aluminum oxide, a molecular sieve, diatomite and silicagel, the active component A is more than one of sulfate ions, phosphate ions and boron oxides, and the active component B is more than one of tungstophosphoric acid, tungstosilicic acid, molybdophosphate, and tungstomolybdic acid. The deacidifying catalyst can help obtain deacidification rate of the crudeoil or the distillate oil above 90%, and acid value of the crude oil or the distillate oil below 0.50mg KOH/g.
Description
Technical field
The invention belongs to the acid reduction method of acid-containing raw oil, particularly a kind of deacidifying catalyst and its production and application.
Background technology
In recent years along with the continuous degree of depth exploitation of crude oil, it is increasing that crude oil with high acid value accounts for the ratio of crude oil total output.The acid of crude oil with high acid value PetroChina Company Limited. comprises aphthenic acids, aliphatic acid and aldehydes matter, wherein naphthenic acid content accounts for more than 95%, aphthenic acids causes serious corrosion to refining equipment in Crude Oil Processing, influence the long period safe handling of oil refining apparatus and the serviceability that influences oil product.In order to reduce acid-containing raw oil corrosivity, satisfy the processing request of oil plant, taked multiple anticorrosive measure both at home and abroad, mainly comprise: (1) height acid number crude oil mixing; (2) add alkali neutralization or depickling from crude oil; (3) filling corrosion inhibiter; (4) upgrade of material etc., these methods have all obtained certain effect, but its scope of application and limitation are also arranged.Patent USP4752381 has introduced a kind of method that adopts in the monoethanolamine and reduce the distillate acid number, but this method does not propose used catalyst, do not having under the catalyst action situation, the acidylate depickling needs higher temperature and excessive organic amine, and depickling tails oleic acid value is still higher, so be difficult to economically bear; Chinese patent 200410048349 has been introduced the method that adopts tin oxide and heteropolyacid catalyst to reduce the distillate acid number, and the acid catalyst that falls that this method is used is SnO or heteropoly acid HPO
4WO
3XH
2O, its method is to use C in the presence of catalyst
1～C
6Alcohol and aphthenic acids esterification deacidification.
Acidylate depickling technology is to be converted into the petroleum acids acid amides by acid of crude oil and distillate PetroChina Company Limited. thereof and organic amine reaction, crude oil and the acid of distillate PetroChina Company Limited. thereof is removed, thereby alleviate the corrosive nature of crude oil and distillate thereof.The petroleum acids acid amides of Sheng Chenging has certain corrosion inhibition in addition, further is reduced in the corrosivity of processing during the crude oil.Therefore, the invention provides a kind of catalyst, under relative temperate condition, use a spot of organic amine just crude oil and the acid of distillate PetroChina Company Limited. thereof can be removed at the acidylate depickling, and with low cost, and flow process simply is easy to realize.
Summary of the invention
Purpose of the present invention just provides a kind of Catalysts and its preparation method and application that is used for the acidylate depickling, uses this catalyst, and the temperature that crude oil and the acid of distillate PetroChina Company Limited. thereof transform and removes relaxes, and petroleum acids removes height.
The invention provides a kind of deacidifying catalyst, it is characterized in that: this catalyst is made up of the active component A of 80～95 weight % carriers, 1～20 weight % and the active component B of 1～20 weight %, in total catalyst weight, wherein carrier is a kind of in aluminium oxide, molecular sieve, diatomite and the silica gel, active component A is more than one in sulfate ion, phosphate anion and the boron oxide compound, preferred one or both, preferred 4～15 weight % of its shared weight percentage in catalyst; Active component B be in tungstophosphoric acid, tungstosilicic acid, molybdophosphate and the tungsten acid more than one, preferably one or both, preferred 1～15 weight % of its shared weight percentage in catalyst.
The invention provides a kind of preparation method of described deacidifying catalyst, the steps include:
1) under 30～60 ℃ temperature, it is in 20～40% the active component aqueous solution that catalyst carrier is immersed in mass concentration, and the amount of carrier is 0.1～0.7 gram in every milliliter of active component aqueous solution, is preferably 0.25～0.5 gram, dip time is 1～10 hour, is preferably 2～4 hours;
2) will flood good catalyst in the step 1), and be preferably 80～120 ℃ and dried 2～12 hours down, be preferably 4～8 hours at 20～150 ℃;
3) with step 2) in the oven dry catalyst at 100～500 ℃, be preferably 250～350 ℃ of following roastings 2～10 hours, best 3～6 hours, be cooled to room temperature and promptly make catalyst of the present invention.
The present invention also provides a kind of application process of described deacidifying catalyst, its method is: the crude oil or the distillate that will contain petroleum acids mix with organic amine, wherein the mol ratio of petroleum acids in crude oil and the distillate and organic amine is 1: 1～1: 1.2, be heated to 80～300 ℃, be preferably 100～180 ℃, then by the reactor of deacidifying catalyst of the present invention is housed, promptly get crude oil or distillate after the depickling.
Reactor of the present invention can be fixed bed reactors, also can be fluidized-bed reactor.When selecting fixed bed reactors for use, its air speed is 0.2～4hr
-1
In the preferred MEA of described organic amine, ethylenediamine and the diethylenetriamine more than one, preferably wherein a kind of.
Can carry out roasting regeneration behind the catalysqt deactivation of the present invention under 300～500 ℃, the active back of recovery is recycling.
Catalyst of the present invention compared with prior art, owing to adopted two kinds of catalyst that component is compound, therefore when being used for the acid of crude oil or distillate PetroChina Company Limited. and organic amine reaction and generating acid amides and carry out the method for depickling, the temperature of depickling reaction is reduced, and the acid removal rate height of crude oil or distillate, generally more than 90%, the acid number of crude oil or distillate can be reduced to below the 0.50mgKOH/g.Thereby reduce the acid number of crude oil or distillate, alleviate the corrosive nature of crude oil or distillate.Catalyst of the present invention in addition has the advantages that raw material is cheap and easy to get, the preparation method is simple, catalytic performance is high.
The specific embodiment
Further specify the present invention below in conjunction with specific embodiment, but embodiment does not limit the scope of the invention.
Embodiment 1
15 gram phosphoric acid, 10 gram boric acid, 15 gram tungstophosphoric acids are dissolved in the 100 gram water; stirring and dissolving evenly back adds 50 gram alumina supports; suction filtration after flooding 3 hours under 40 ℃ of conditions; under 110 ℃ of temperature dry 6 hours then; high-temperature roasting 4 hours under 300 ℃ of temperature, nitrogen protection at last; promptly obtain deacidifying catalyst A after the cooling, measuring active component content is 9.6 weight %.
Embodiment 2
20 gram ammonium sulfate, 20 gram boric acid, 25 gram tungstosilicic acids are dissolved in the 100 gram water, and stirring and dissolving evenly back adds 50 gram diatomite supports, and the preparation method is identical with embodiment 1, promptly obtains deacidifying catalyst B after the cooling, and measuring active component content is 19.5 weight %.
Embodiment 3
10 gram phosphoric acid, 5 gram boric acid, 10 gram tungstosilicic acids are dissolved in the 100 gram water, and stirring and dissolving evenly back adds 50 gram diatomite supports, and the preparation method is identical with embodiment 1, makes deacidifying catalyst C, and measuring active component content is 5.2 weight %.
Embodiment 4
According to method like the preparation deacidifying catalyst category-A among the embodiment 1, replace tungstosilicic acid by molybdophosphate, obtain deacidifying catalyst D after the cooling.
Embodiment 5
According to method like the preparation deacidifying catalyst category-A among the embodiment 1, replace alumina support by the inorganic silica gel carrier, obtain deacidifying catalyst E after the cooling.
Embodiment 6
20 gram phosphoric acid, 15 gram tungstophosphoric acids, 10 gram molybdophosphates are dissolved in the 100 gram water; stirring and dissolving evenly back adds 50 gram alumina supports; suction filtration after flooding 3 hours under 40 ℃ of conditions; under 110 ℃ of temperature dry 6 hours then; high-temperature roasting 4 hours under 500 ℃ of temperature, nitrogen protection at last; promptly obtain deacidifying catalyst F after the cooling, measuring active component content is 12.5 weight %.
Embodiment 7
15 gram ammonium sulfate, 10 gram boric acid, 15 gram tungstosilicic acids, 10 gram tungsten acid are dissolved in the 100 gram water, stirring and dissolving evenly back adds 50 gram diatomite supports, the preparation method is identical with embodiment 1, promptly obtains deacidifying catalyst G after the cooling, and measuring active component content is 15.2 weight %.
Embodiment 8
According to the similar method of preparation deacidifying catalyst F among the embodiment 6, replace alumina support by diatomite support, obtain deacidifying catalyst H after the cooling.
Embodiment 9
Deacidifying catalyst A packs in the 100mL fixed bed reactors, use the measuring pump charging, feedstock oil is domestic high-acid crude oil, acid number is 3.6mg KOH/g, organic amine is a monoethanolamine, addition is 0.39 weight % (petroleum acids and organic amine mol ratio are 1/1), earlier crude oil is mixed with monoethanolamine, measuring pump is by the beds of reactor then, and reaction condition is: 160 ℃ of temperature, pressure 0.15MPa, air speed is 1hr-1, stable operation is sample analysis after 10 hours, records that the acid number of crude oil is 0.32mg KOH/g after the depickling, and removal efficiency is 91.1%.
Contrast test: in reactor, add alumina support, 160 ℃ of temperature, pressure 0.15MPa, air speed is 1hr
-1Stable operation is after 10 hours under the condition, records that the acid number of crude oil is 3.0mg KOH/g after the depickling, and removal efficiency is 16.7%.
Embodiment 10～22
According to similar method among the embodiment 9, investigate the catalytic performance of deacidifying catalyst B, deacidifying catalyst C, deacidifying catalyst D, deacidifying catalyst E, deacidifying catalyst F, deacidifying catalyst G and deacidifying catalyst H respectively, and the catalytic performance of several catalyst when using diethylenetriamine as organic amine, result of the test sees Table 1.
Table 1 deacidifying catalyst is to the catalytic performance of crude oil deacidification
| Sequence number | Deacidifying catalyst | Organic amine | Acid/amine mol ratio | Acid value for crude oil mg KOH/g after the depickling | Acid removal rate % |
| 1 | A | Monoethanolamine | 1/1 | 0.32 | 91.1 |
| 2 | B | Monoethanolamine | 1/1 | 0.28 | 92.2 |
| 3 | C | Monoethanolamine | 1/1 | 0.32 | 91.1 |
| 4 | D | Monoethanolamine | 1/1 | 0.29 | 91.9 |
| 5 | E | Monoethanolamine | 1/1 | 0.33 | 90.8 |
| 6 | F | Monoethanolamine | 1/1 | 0.35 | 90.3 |
| 7 | G | Monoethanolamine | 1/1 | 0.33 | 90.8 |
| 8 | H | Monoethanolamine | 1/1 | 0.34 | 90.6 |
| 9 | Aluminium oxide | Monoethanolamine | 1/1 | 3.0 | 16.7 |
| 10 | Diatomite | Monoethanolamine | 1/1 | 2.8 | 22.2 |
| 11 | Inorganic silica gel | Monoethanolamine | 1/1 | 3.0 | 16.7 |
| 12 | A | Diethylenetriamine | 1/1 | 0.26 | 92.7 |
| 13 | B | Diethylenetriamine | 1/1 | 0.25 | 93.0 |
| 14 | C | Diethylenetriamine | 1/1 | 0.27 | 92.5 |
| 15 | D | Diethylenetriamine | 1/1 | 0.28 | 92.2 |
| 16 | E | Diethylenetriamine | 1/1 | 0.30 | 91.7 |
| 17 | F | Diethylenetriamine | 1/1 | 0.33 | 90.8 |
| 18 | Aluminium oxide | Diethylenetriamine | 1/1 | 3.0 | 16.7 |
| 19 | Diatomite | Diethylenetriamine | 1/1 | 3.2 | 11.1 |
| 20 | Inorganic silica gel | Diethylenetriamine | 1/1 | 3.2 | 11.1 |
Claims (14)
1. deacidifying catalyst, it is characterized in that: this catalyst is made up of the active component A of 80～95 weight % carriers, 1～20 weight % and the active component B of 1～20 weight %, carrier, active component A and active component B three weight sum equal 100 weight %, in total catalyst weight, wherein carrier is a kind of in aluminium oxide, molecular sieve, diatomite and the silica gel, active component A is more than one in sulfate ion, phosphate anion and the boron oxide compound, active component B be in tungstophosphoric acid, tungstosilicic acid and the molybdophosphate more than one.
2. deacidifying catalyst according to claim 1 is characterized in that: catalyst activity component A is one or both in sulfate ion, phosphate anion and the boron oxide compound.
3. deacidifying catalyst according to claim 1 is characterized in that: the catalyst activity B component is one or both in tungstophosphoric acid, tungstosilicic acid and the molybdophosphate.
4. according to claim 1 or 2 or 3 described deacidifying catalysts, it is characterized in that: catalyst activity component A accounts for total catalyst weight 4～15 weight %, and carrier, active component A and active component B three weight sum equal 100 weight %.
5. according to claim 1 or 2 or 3 described deacidifying catalysts, it is characterized in that: the catalyst activity B component accounts for total catalyst weight 1～15 weight %, and carrier, active component A and active component B three weight sum equal 100 weight %.
6. the preparation method of the described deacidifying catalyst of claim 1, it is characterized in that: the step of this method is:
1) under 30～60 ℃ temperature, it is in 20～40% the active component aqueous solution that catalyst carrier is immersed in mass concentration, and the amount of carrier is 0.1～0.7 gram in every milliliter of active component aqueous solution, and dip time is 1～10 hour;
2) dipping in the step 1) is good catalyst was dried 2～12 hours under 20～150 ℃ of temperature;
3) with step 2) in the catalyst of oven dry 100～500 ℃ of roasting temperatures 2～10 hours, be cooled to room temperature and promptly make deacidifying catalyst.
7. preparation method according to claim 6 is characterized in that: in the step 1) in every milliliter of active component aqueous solution the amount of carrier be 0.25～0.5 gram, dip time is 2～4 hours.
8. preparation method according to claim 6 is characterized in that: step 2) in bake out temperature be 80～120 ℃, drying time is 4～8 hours.
9. preparation method according to claim 6 is characterized in that: sintering temperature is 250～350 ℃ in the step 3), and roasting time is 3～6 hours.
10. the application of the described deacidifying catalyst of claim 1, it is characterized in that: the crude oil or the distillate that will contain petroleum acids mix with organic amine, wherein the mol ratio of petroleum acids and organic amine is 1: 1～1: 1.2, be heated to 80～300 ℃, then by the reactor of the described deacidifying catalyst of claim 1 is housed, promptly get crude oil or distillate after the depickling.
11. application according to claim 10 is characterized in that: described heating-up temperature is 100～180 ℃.
12. application according to claim 10 is characterized in that: described organic amine is more than one in MEA, ethylenediamine and the diethylenetriamine.
13. application according to claim 10 is characterized in that: described organic amine is a kind of in MEA, ethylenediamine and the diethylenetriamine.
14. application according to claim 10 is characterized in that: the deacidifying catalyst behind the inactivation carries out roasting regeneration under 300～500 ℃, and the active back of recovery is recycling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100647114A CN101537363B (en) | 2009-04-24 | 2009-04-24 | Deacidifying catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100647114A CN101537363B (en) | 2009-04-24 | 2009-04-24 | Deacidifying catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101537363A CN101537363A (en) | 2009-09-23 |
| CN101537363B true CN101537363B (en) | 2011-01-12 |
Family
ID=41120883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100647114A Active CN101537363B (en) | 2009-04-24 | 2009-04-24 | Deacidifying catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101537363B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104492412B (en) * | 2015-01-07 | 2016-08-24 | 苏珂 | A kind of preparation method of oil deacidifying catalyst |
| CN108192728A (en) * | 2017-12-29 | 2018-06-22 | 常州市蓝勖化工有限公司 | The preparation method of one vegetable oil deacidification agent |
| CN110106742B (en) * | 2019-05-30 | 2020-07-14 | 复旦大学 | Slow-release alkaline molecular sieve deacidification agent and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073429A (en) * | 1992-10-26 | 1993-06-23 | 厦门大学 | The preparation method of applying dioxan aminoethyl alcohol carboxylic ether |
| CN1445019A (en) * | 2003-03-28 | 2003-10-01 | 哈尔滨工程大学 | Carboxylic ester synthesized by sulfuric acid-heteropoly acid (salt) admixture catalyst system |
| CN1715369A (en) * | 2004-06-29 | 2006-01-04 | 中国石油化工股份有限公司 | Esterizing acid lowering method for acid containing raw oil or fraction oil |
-
2009
- 2009-04-24 CN CN2009100647114A patent/CN101537363B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073429A (en) * | 1992-10-26 | 1993-06-23 | 厦门大学 | The preparation method of applying dioxan aminoethyl alcohol carboxylic ether |
| CN1445019A (en) * | 2003-03-28 | 2003-10-01 | 哈尔滨工程大学 | Carboxylic ester synthesized by sulfuric acid-heteropoly acid (salt) admixture catalyst system |
| CN1715369A (en) * | 2004-06-29 | 2006-01-04 | 中国石油化工股份有限公司 | Esterizing acid lowering method for acid containing raw oil or fraction oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101537363A (en) | 2009-09-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101116816A (en) | Method for preparing load type rhodium catalyst for making high-carbon aldehyde using hydroformylation of higher olefins | |
| CN108623457A (en) | The catalytic decomposition process of formic acid | |
| CN105777523B (en) | A kind of method for preparing lactic acid under temperate condition by carbohydrate | |
| CN101537363B (en) | Deacidifying catalyst and preparation method and application thereof | |
| CN109833897B (en) | Catalyst for producing furfuryl alcohol, preparation method thereof and method for producing furfuryl alcohol | |
| CN103055937A (en) | Preparation method of immobilized ionic liquid used for ester exchange reaction | |
| CN103626633A (en) | Method for promoting solid catalyst to depolymerize cellulose | |
| CN102008938A (en) | Naphtha denitrification adsorbent and preparation method thereof | |
| CN103159587A (en) | Application for catalyst in hydrocracking for biological polyol | |
| CN104399513A (en) | Toluene-methanol side chain alkylation catalyst and preparation method thereof | |
| CN103418365B (en) | A kind of preparation of solid base catalyst and the application in production of biodiesel thereof | |
| CN104525269A (en) | Supported heteropoly-acid solid catalyst used for esterification of pentaerythritol, and preparation method and application thereof | |
| CN101559365B (en) | Preparation and application of supported silver catalyst | |
| CN108620137A (en) | The preparation process of organic compound depickling catalyst | |
| CN105170199B (en) | A kind of regeneration method of coal gasification waste water deep oxidation catalyst | |
| CN113477247B (en) | High-activity hydrothermal-resistant stable catalyst and preparation method thereof | |
| CN101249448B (en) | Catalyst for methanol dewatering for preparing dimethyl ether and preparation method thereof | |
| CN107910565B (en) | Preparation method of monatomic cobalt/graphene proton exchange membrane fuel cell catalyst | |
| CN102452933A (en) | Preparation method of carboxylic ester | |
| CN103143339B (en) | Preparation method of solid base catalyst, and application of solid base catalyst in catalytic preparation of biodiesel | |
| CN102190543A (en) | Method for preparing ethylene by dehydrating ethanol | |
| CN110295068A (en) | Utilize the method for Catalyzed by Heteropolyacid Supported on Actived Carbon agent biodiesel synthesis | |
| CN112827509A (en) | Preparation method of modified AlSBA supported acidic ionic liquid catalyst | |
| CN110437892A (en) | A kind of biodiesel preparation process | |
| CN103421613A (en) | Preparation method for environment-friendly hydraulic oil base oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Co-patentee after: Luoyang Petrochemical Engineering Corporation /SINOPEC Patentee after: China Petrochemical Group Corp. Address before: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Co-patentee before: Luoyang Petrochemical Engineering Co., China Petrochemical Group Patentee before: China Petrochemical Group Corp. |
|
| ASS | Succession or assignment of patent right |
Free format text: FORMER OWNER: SINOPEC LUOYANG PETROCHEMICAL ENGINEERING CORPORATION Effective date: 20130326 Owner name: SINOPEC LUOYANG PETROCHEMICAL ENGINEERING CORPORAT Free format text: FORMER OWNER: SINOPEC GROUP Effective date: 20130326 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 100728 CHAOYANG, BEIJING TO: 471003 LUOYANG, HENAN PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20130326 Address after: 471003 Zhongzhou West Road, Henan, China, No. 27, No. Patentee after: Luoyang Petrochemical Engineering Corporation /SINOPEC Address before: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Patentee before: China Petrochemical Group Corp. Patentee before: Luoyang Petrochemical Engineering Corporation /SINOPEC |