A kind of preparation method of oil deacidifying catalyst
Technical field
The invention belongs to petrolization catalyst preparation technical field, be specifically related to the preparation method of a kind of oil deacidifying catalyst.
Background technology
Along with the day by day exhausted of petroleum resources and the continuous increase of recovery percent, a large amount of crude oil with high acid value are extracted, and the most annual high-acid crude oil yield accounts for about the 5% of total output, and annual the most also with 0.3% speed increment.High-acid crude oil is the crude oil that a kind of viscosity is high, density is big, colloid is many, acid number is high and carbon residue is high.Crude oil with high acid value resource about 900,000,000,000 tons in the world, allowable exploitation about 180,000,000,000 tons.China's crude oil with high acid value resource is the abundantest, is mainly distributed on the oil fields such as the Liaohe River, triumph, Xinjiang.Acid value for crude oil size reflects the number of the petroleum acids such as aphthenic acids in crude oil, fatty acid and phenols.When acid value for crude oil (in terms of KOH, lower same), more than 0.5 mg/g, can cause equipment corrosion, therefore generally more than 0.5 mg/g crude oil, acid number is referred to as crude oil with high acid value.Crude oil processing technique routinely carrys out processing highly acid crude oil, will cause heating furnace, fractionating column and equipment installation corrosion, and affect product quality.Therefore, oil refining enterprise does not the most favor in processing highly acid crude oil, and drug on the market to cause high-acid crude oil on international raw oil market, and price is the most on the low side.The successful research and development of high-acid crude oil deacidification new technology, must produce preferable economic benefit, the most more efficiently remove aphthenic acids from crude oil and are of great significance by tool.
The oil deacidification route used the most both at home and abroad, mainly has two big classes, and a kind of is the destructive carboxyl removing naphthenic acid molecule;Another kind is by aphthenic acids overall separation and to recycle aphthenic acids resource.The crude oil deacidification route of destructive removing naphthenic acid molecule carboxyl mainly has: catalytic hydrogenation deacidification, non-hydrogen catalytic deacidification, non-hydrogen pyrolysis deacidification, fluid catalytic cracking etc..It is separated and recovered from utilizing the technique of aphthenic acids resource mainly to have from crude oil by aphthenic acids entirety: chemical reaction separates the methods such as (chemical extraction), adsorbing separation, solvent extraction separation and membrance separation.Although these methods have certain deacidification, but most of deacidification is thorough, and complex technical process, and the most highly desirable developing a kind of has higher deacidification performance and deacidification deacidifying catalyst simple to operate.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of oil deacidifying catalyst to overcome above the deficiencies in the prior art, strengthen deacidification efficiency and the viscosity-reducing performance of catalyst.
The present invention is realized by techniques below means:
The preparation method of a kind of oil deacidifying catalyst, comprises the following steps:
Step one; by weight, by polyester resin 5~10 parts, Polyethylene Glycol 3~8 parts and acetic anhydride 2~6 parts join in 10~20 parts of dehydrated alcohol; it is uniformly mixed; then proceed in retort, under the conditions of inert gas shielding, intensification carbonization; then room temperature it is down to; residue after carbonization uses ammonia clean up with deionized water after soaking 10~20 minutes again, and being ground to particle diameter after drying is 800~1000 μm, obtains carbon microspheres;
Step 2, by weight, mixes carbon microspheres 10~15 parts with 5~10 parts of Biformyls, is heated to 50~60 DEG C under vacuum, keeps 20~30 minutes, then by sucking filtration desolvation, is dried by carbon microspheres;
Step 3, by weight the carbon microspheres 10 after step 2 drying~20 parts are joined in reactor, add calcium oxide 1~3 parts, Barium monoxide 1~3 parts, zinc sulfate 2~4 parts, oxirane 2~5 parts, trimethylamine 1~3 parts, it is heated to 150~180 DEG C under vacuum, stirs 20~30 minutes, be down to room temperature;
Step 4, mixture step 3 obtained is sintered, sintering temperature is 1000~1100 DEG C, in sintering process, is first warming up to 200~220 DEG C, it is incubated 40~60 minutes, it is warming up to 600~650 DEG C again, keeps 10~20 minutes, then heat to 1000~1100 DEG C, keep 150~200 minutes, be down to room temperature;
Step 5, the sinter grind into powder that step 4 is obtained, obtain oil deacidifying catalyst.
The preparation method of described oil deacidifying catalyst, in step one, Polyethylene Glycol can be Macrogol 600 or polyethylene glycol-800.
The preparation method of described oil deacidifying catalyst, in step one, noble gas can be nitrogen or argon.
The preparation method of described oil deacidifying catalyst, in step one, carbonization temperature can be 800~900 DEG C.
The preparation method of described oil deacidifying catalyst, in step one, the mass concentration of ammonia can be 30~33%.
The preparation method of described oil deacidifying catalyst, in step one, drying condition can be to dry temperature 100~120 DEG C, drying time 3~4h.
The preparation method of described oil deacidifying catalyst, in step 2, the vacuum of vacuum condition can be 0.01~0.04MPa.
The preparation method of described oil deacidifying catalyst, in step 3, the vacuum of vacuum condition can be 0.01~0.02MPa.
The preparation method of described oil deacidifying catalyst, the programming rate being warming up to 600~650 DEG C in step 4 can be 20~30 DEG C/min, the programming rate being warming up to 1000~1100 DEG C can be 50~60 DEG C/min, and the cooling rate being down to room temperature can be 30~40 DEG C/min.
The oil deacidifying catalyst that the present invention provides has good deacidification and viscosity reduction effect, and wherein catalyst charge is under conditions of 0.2%, and during reaction temperature 250 DEG C, acid removal rate can reach more than 95.2%;During reaction temperature 300 DEG C, acid removal rate can reach more than 97.2%;During reaction temperature 350 DEG C, acid removal rate can reach more than 98.5%, it is possible to reaches good deacidification under the conditions of relatively low reaction temperatures, also has the viscosity reduction effect of excellence simultaneously.
Detailed description of the invention
Embodiment 1
The preparation method of a kind of oil deacidifying catalyst, comprises the following steps:
Step one; by weight; by 5 parts of polyester resin; Macrogol 600 3 parts and acetic anhydride 2 parts join in 10 parts of dehydrated alcohol; it is uniformly mixed; then proceed in retort; under nitrogen protective condition, intensification carbonization, carbonization temperature is 800 DEG C; then room temperature it is down to; the ammonia using mass concentration to be 30% residue after carbonization cleans up with deionized water after soaking 10 minutes again, and being ground to particle diameter after drying is 800 μm, obtains carbon microspheres; wherein drying temperature is 100 DEG C, drying time 4h;
Step 2, by weight, mixes carbon microspheres 10 parts with 5 parts of Biformyls, is heated to 50 DEG C under vacuum is 0.01MPa, keeps 20 minutes, then by sucking filtration desolvation, is dried by carbon microspheres;
Step 3, the carbon microspheres 10 parts after step 2 being dried by weight joins in reactor, adds calcium oxide 1 part, Barium monoxide 1 part, 2 parts of zinc sulfate, 2 parts of oxirane, trimethylamine 1 part, under vacuum is 0.01MPa, it is heated to 150 DEG C, stirs 20 minutes, be down to room temperature;
Step 4, mixture step 3 obtained is sintered, and sintering temperature is 1000 DEG C, in sintering process, is first warming up to 200 DEG C, is incubated 40 minutes, then is warming up to 600 DEG C, keeps 10 minutes, then heats to 1000 DEG C, keeps 150 minutes, is down to room temperature;The programming rate being wherein warming up to 600 DEG C is 20 DEG C/min, and the programming rate being warming up to 1000 DEG C is 50 DEG C/min, and the cooling rate being down to room temperature is 30 DEG C/min;
Step 5, the sinter grind into powder that step 4 is obtained, obtain oil deacidifying catalyst.
Embodiment 2
The preparation method of a kind of oil deacidifying catalyst, comprises the following steps:
Step one; by weight; by 6 parts of polyester resin; polyethylene glycol-800 5 parts and acetic anhydride 3 parts join in 13 parts of dehydrated alcohol; it is uniformly mixed; then proceed in retort; under the conditions of argon shield, intensification carbonization, carbonization temperature is 830 DEG C; then room temperature it is down to; the ammonia using mass concentration to be 31% residue after carbonization cleans up with deionized water after soaking 12 minutes again, and being ground to particle diameter after drying is 850 μm, obtains carbon microspheres; wherein drying temperature is 105 DEG C, drying time 3h;
Step 2, by weight, mixes carbon microspheres 12 parts with 6 parts of Biformyls, is heated to 54 DEG C under vacuum is 0.02MPa, keeps 25 minutes, then by sucking filtration desolvation, is dried by carbon microspheres;
Step 3, the carbon microspheres 13 parts after step 2 being dried by weight joins in reactor, adds calcium oxide 1 part, Barium monoxide 2 parts, 2 parts of zinc sulfate, 3 parts of oxirane, trimethylamine 2 parts, under vacuum is 0.02MPa, it is heated to 160 DEG C, stirs 23 minutes, be down to room temperature;
Step 4, mixture step 3 obtained is sintered, and sintering temperature is 1050 DEG C, in sintering process, first it is warming up to 210 DEG C, is incubated 48 minutes, it is warming up to 620 DEG C again, keep 13 minutes, then heat to 1040 DEG C, keep 160 minutes, it is down to room temperature, the programming rate being wherein warming up to 620 DEG C is 25 DEG C/min, and the programming rate being warming up to 1040 DEG C is 54 DEG C/min, and the cooling rate being down to room temperature is 35 DEG C/min;
Step 5, the sinter grind into powder that step 4 is obtained, obtain oil deacidifying catalyst.
Embodiment
3
The preparation method of a kind of oil deacidifying catalyst, comprises the following steps:
Step one; by weight; by 8 parts of polyester resin; Macrogol 600 7 parts and acetic anhydride 5 parts join in 16 parts of dehydrated alcohol; it is uniformly mixed; then proceed in retort; under nitrogen protective condition, intensification carbonization, carbonization temperature is 880 DEG C; then room temperature it is down to; the ammonia using mass concentration to be 32% residue after carbonization cleans up with deionized water after soaking 18 minutes again, and being ground to particle diameter after drying is 900 μm, obtains carbon microspheres; wherein drying temperature is 112 DEG C, drying time 4h;
Step 2, by weight, mixes carbon microspheres 13 parts with 7 parts of Biformyls, is heated to 56 DEG C under vacuum is 0.03MPa, keeps 28 minutes, then by sucking filtration desolvation, is dried by carbon microspheres;
Step 3, the carbon microspheres 18 parts after step 2 being dried by weight joins in reactor, adds calcium oxide 2 parts, Barium monoxide 2 parts, 3 parts of zinc sulfate, 4 parts of oxirane, trimethylamine 2 parts, under vacuum is 0.02MPa, it is heated to 170 DEG C, stirs 28 minutes, be down to room temperature;
Step 4, mixture step 3 obtained is sintered, and sintering temperature is 1080 DEG C, in sintering process, first it is warming up to 215 DEG C, is incubated 55 minutes, it is warming up to 640 DEG C again, keep 18 minutes, then heat to 1100 DEG C, keep 180 minutes, it is down to room temperature, the programming rate being wherein warming up to 640 DEG C is 30 DEG C/min, and the programming rate being warming up to 1100 DEG C is 55 DEG C/min, and the cooling rate being down to room temperature is 40 DEG C/min;
Step 5, the sinter grind into powder that step 4 is obtained, obtain oil deacidifying catalyst.
Embodiment
4
The preparation method of a kind of oil deacidifying catalyst, comprises the following steps:
Step one; by weight; by 10 parts of polyester resin; polyethylene glycol-800 8 parts and acetic anhydride 6 parts join in 20 parts of dehydrated alcohol; it is uniformly mixed; then proceed in retort; under nitrogen protective condition, intensification carbonization, carbonization temperature is 900 DEG C; then room temperature it is down to; the ammonia using mass concentration to be 33% residue after carbonization cleans up with deionized water after soaking 20 minutes again, and being ground to particle diameter after drying is 1000 μm, obtains carbon microspheres; wherein drying temperature is 120 DEG C, drying time 4h;
Step 2, by weight, mixes carbon microspheres 15 parts with 10 parts of Biformyls, is heated to 60 DEG C under vacuum is 0.04MPa, keeps 30 minutes, then by sucking filtration desolvation, is dried by carbon microspheres;
Step 3, the carbon microspheres 20 parts after step 2 being dried by weight joins in reactor, adds calcium oxide 3 parts, Barium monoxide 3 parts, 4 parts of zinc sulfate, 5 parts of oxirane, trimethylamine 3 parts, under vacuum is 0.02MPa, it is heated to 180 DEG C, stirs 30 minutes, be down to room temperature;
Step 4, mixture step 3 obtained is sintered, and sintering temperature is 1100 DEG C, in sintering process, first it is warming up to 220 DEG C, is incubated 60 minutes, it is warming up to 650 DEG C again, keep 20 minutes, then heat to 1100 DEG C, keep 200 minutes, it is down to room temperature, the programming rate being wherein warming up to 650 DEG C is 30 DEG C/min, and the programming rate being warming up to 1100 DEG C is 60 DEG C/min, and the cooling rate being down to room temperature is 40 DEG C/min;
Step 5, the sinter grind into powder that step 4 is obtained, obtain oil deacidifying catalyst.
Comparative example
1
The preparation method of a kind of oil deacidifying catalyst, comprises the following steps:
Step one; by weight; by 8 parts of polyester resin; Macrogol 600 7 parts and acetic anhydride 5 parts join in 16 parts of dehydrated alcohol; it is uniformly mixed; then proceed in retort; under nitrogen protective condition, intensification carbonization, carbonization temperature is 880 DEG C; then room temperature it is down to; the ammonia using mass concentration to be 32% residue after carbonization cleans up with deionized water after soaking 18 minutes again, and being ground to particle diameter after drying is 900 μm, obtains carbon microspheres; wherein drying temperature is 112 DEG C, drying time 4h;
Step 2, the carbon microspheres after step one being dried by weight 18 parts joins in reactor, adds calcium oxide 2 parts, Barium monoxide 2 parts, 3 parts of zinc sulfate, 4 parts of oxirane, trimethylamine 2 parts, under vacuum is 0.02MPa, it is heated to 170 DEG C, stirs 28 minutes, be down to room temperature;
Step 3, mixture step 2 obtained is sintered, and sintering temperature is 1080 DEG C, in sintering process, first it is warming up to 215 DEG C, is incubated 55 minutes, it is warming up to 640 DEG C again, keep 18 minutes, then heat to 1100 DEG C, keep 180 minutes, it is down to room temperature, the programming rate being wherein warming up to 640 DEG C is 30 DEG C/min, and the programming rate being warming up to 1100 DEG C is 55 DEG C/min, and the cooling rate being down to room temperature is 40 DEG C/min;
Step 4, the sinter grind into powder that step 3 is obtained, obtain oil deacidifying catalyst.
Comparative example
2
The preparation method of a kind of oil deacidifying catalyst, comprises the following steps:
Step one; by weight; by 8 parts of polyester resin; Macrogol 600 7 parts and acetic anhydride 5 parts join in 16 parts of dehydrated alcohol; it is uniformly mixed; then proceed in retort; under nitrogen protective condition, intensification carbonization, carbonization temperature is 880 DEG C; then room temperature it is down to; the ammonia using mass concentration to be 32% residue after carbonization cleans up with deionized water after soaking 18 minutes again, and being ground to particle diameter after drying is 900 μm, obtains carbon microspheres; wherein drying temperature is 112 DEG C, drying time 4h;
Step 2, by weight, mixes carbon microspheres 13 parts with 7 parts of Biformyls, is heated to 56 DEG C under vacuum is 0.03MPa, keeps 28 minutes, then by sucking filtration desolvation, is dried by carbon microspheres;
Step 3, the carbon microspheres 18 parts after step 2 being dried by weight joins in reactor, adds calcium oxide 2 parts, Barium monoxide 2 parts, 3 parts of zinc sulfate, is heated to 170 DEG C, stirs 28 minutes, be down to room temperature under vacuum is 0.02MPa;
Step 4, mixture step 3 obtained is sintered, and sintering temperature is 1080 DEG C, in sintering process, first it is warming up to 215 DEG C, is incubated 55 minutes, it is warming up to 640 DEG C again, keep 18 minutes, then heat to 1100 DEG C, keep 180 minutes, it is down to room temperature, the programming rate being wherein warming up to 640 DEG C is 30 DEG C/min, and the programming rate being warming up to 1100 DEG C is 55 DEG C/min, and the cooling rate being down to room temperature is 40 DEG C/min;
Step 5, the sinter grind into powder that step 4 is obtained, obtain oil deacidifying catalyst.
The oil deacidifying catalyst using above example and comparative example to prepare carries out the test of deacidification effect, and process is as follows:
Being 13mgKOH/g by acid number, viscosity is 850mm2/ s(50 DEG C) without dehydration and the petroleum crude oil 10L of desalination, join in reactor, the oil deacidifying catalyst 20g that addition above example and comparative example obtain, stirring reaction 3h the most at different temperatures, the acid number of crude oil is tested after reaction, calculate acid removal rate, concrete outcome such as table 1 below~table 3:
Acid removal rate and viscosity test is reacted under the conditions of 1 250 DEG C of table
Project |
Acid removal rate/% |
Viscosity of crude (50 DEG C)/mm after deacidification2/s |
Embodiment 1 |
95.2 |
91.5 |
Embodiment 2 |
96.3 |
88.6 |
Embodiment 3 |
96.8 |
86.3 |
Embodiment 4 |
95.7 |
87.8 |
Comparative example 1 |
76.3 |
363.6 |
Comparative example 2 |
82.5 |
402.8 |
Acid removal rate and viscosity test is reacted under the conditions of 2 300 DEG C of table
Project |
Acid removal rate/% |
Viscosity of crude (50 DEG C)/mm after deacidification2/s |
Embodiment 1 |
97.2 |
86.7 |
Embodiment 2 |
98.8 |
84.2 |
Embodiment 3 |
99.4 |
82.5 |
Embodiment 4 |
99.1 |
83.6 |
Comparative example 1 |
78.5 |
342.8 |
Comparative example 2 |
85.6 |
389.4 |
Acid removal rate and viscosity test is reacted under the conditions of 3 350 DEG C of table
Project |
Acid removal rate/% |
Viscosity of crude (50 DEG C)/mm after deacidification2/s |
Embodiment 1 |
98.5 |
84.5 |
Embodiment 2 |
99.5 |
83.7 |
Embodiment 3 |
99.8 |
82.2 |
Embodiment 4 |
99.3 |
83.4 |
Comparative example 1 |
79.7 |
336.6 |
Comparative example 2 |
88.5 |
388.2 |
From above test data it can be seen that the oil deacidifying catalyst that the present invention provides has good deacidification and viscosity reduction effect, wherein catalyst charge is under conditions of 0.2%, and during reaction temperature 250 DEG C, acid removal rate can reach more than 95.2%;During reaction temperature 300 DEG C, acid removal rate can reach more than 97.2%;During reaction temperature 350 DEG C, acid removal rate can reach more than 98.5%, it is possible to reaches good deacidification under the conditions of relatively low reaction temperatures.Comparative example 1 and comparative example 2 are the further proving tests carried out on the basis of embodiment 3, comparative example 1 does not wherein carry out the addition glyoxal reaction of embodiment 3 step 2, other are same as in Example 3, result causes acid removal rate and viscosity-reducing performance to have significantly reduction, as can be seen here, preparation process two processes the catalytic performance for final products by Biformyl to carbon microspheres important potentiation.Comparative example 2 does not add in preparation process three oxirane and trimethylamine, other are same as in Example 3, result causes acid removal rate to be decreased obviously with Viscosity-reducing, but it is compared with comparative example 1, acid removal rate declines less, and viscosity-reducing performance reduces relatively big, it can be said that the viscosity-reducing performance for final products that introduces of bright both components has further potentiation.