CN103386323A - Quality-improving and viscosity-reducing catalyst and preparation method thereof - Google Patents
Quality-improving and viscosity-reducing catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a quality-improving and viscosity-reducing catalyst and a preparation method thereof. The method comprises the following steps: (1) in an air atmosphere, performing a reaction on petroleum distillate and transition metal inorganic salt; and (2) after reaction in the step (1), adding sodium hydroxide or potassium hydroxide to a reaction system of the reaction for continuous reaction, thereby obtaining the quality-improving and viscosity-reducing catalyst after reaction. Raw materials in the preparation method disclosed by the invention are originated from petroleum, so that the catalyst is good in intermiscibility with thickened oil, and has good universality. The synthetic raw materials (petroleum distillate and air) are wide in source, and the catalyst is high in catalytic activity, simple in production process and low in cost, and has good applicability and wide market prospect for improving the thickened oil recovery efficiency.
Description
Technical field
The present invention relates to a kind of upgrading viscosity reduction Catalysts and its preparation method.
Background technology
China's viscous crude aboundresources.According to statistics, China has successively found more than 70 viscous crude field in 12 basins, has set up 5 great development production areas, and output has accounted for 10% of national oil total output, and viscous crude is just being played the part of more and more important role in China's energy resource structure.But the viscous crude molecular structure is complicated, and heavy constituent content is high, and viscosity is high, and its exploitation is still world-famous puzzle so far, to such an extent as to a lot of viscous crude resource is difficult to exploitation.
Under heavy oil wells, upgrading viscosity reduction technology is a kind of new technology that is derived on thickened oil steam-stimulated basis.Compare with other the Technology of Heavy Oil Recoveries, down-hole upgrading viscosity reduction technology can be cracked into little molecule with the part heavy constituent in viscous crude, and the viscosity of irreversible reduction crude oil has improved the quality of viscous crude.This technology is applied widely, and the super viscous crude resource of spy that present steam soak technology is difficult to exploit has effect preferably, and this key problem in technology is the development of catalytic pyrolysis viscosity reduction catalyst.
What the down-hole upgrading viscosity reduction catalyst of report generally adopted at present is all the transition metal salt of petroleum naphthenic acid and aliphatic acid.The preparation of aliphatic acid transition metal salt comprises the preparation of aliphatic acid and the preparation of aliphatic acid transition metal salt, the preparation technology of aliphatic acid comprises oxidation-saponification-separation-acidifying-distillation, and the preparation technology of aliphatic acid transition metal salt comprises saponification-metathesis reaction-separation-drying.The preparation of the preparation of above-mentioned aliphatic acid and aliphatic acid transition metal salt is independent operation separately, and production technology can not continued operation, and intermediate link and follow-up lock out operation are complicated, but also can produce a large amount of waste water.
Summary of the invention
The purpose of this invention is to provide a kind of upgrading viscosity reduction Catalysts and its preparation method, upgrading viscosity reduction catalyst provided by the invention is the viscosity reduction catalyst that a kind of catalytic activity is high, oil-soluble good, heat resistance is good, can be used for upgrading viscosity reduction under the catalysis heavy oil wells, thereby improve thick oil recovery ratio.
The preparation method of a kind of upgrading viscosity reduction catalyst provided by the present invention, comprise the steps:
(1) in air atmosphere, fraction oil of petroleum and transition metal inorganic salts react;
(2) after reacting completely described in step (1),, to adding in the reaction system of described reaction NaOH or potassium hydroxide to continue reaction, react after complete and namely obtain described upgrading viscosity reduction catalyst.
In above-mentioned preparation method, described fraction oil of petroleum can be kerosene, diesel oil, vacuum 1st side cut distillate, Light lube oil, subtracts three line distillates and subtract in four line distillates at least a;
The boiling range of described vacuum 1st side cut distillate is 210～340 ℃; The boiling range of described Light lube oil is 280～360 ℃; The described boiling range that subtracts three line distillates is 360～430 ℃, and the described boiling range that subtracts four line distillates is 420～500 ℃.
In above-mentioned preparation method, described transition metal inorganic salts can be in ferric sulfate, manganese sulfate, zinc sulfate, copper sulphate, cobaltous sulfate, vanadic sulfate, molybdenum trisulfate and nickelous sulfate at least a.
In above-mentioned preparation method, in step (1), described fraction oil of petroleum and described transition metal inorganic salts mass ratio can be 10:1～2, specifically can be 10:1.5～2,10:1.5,10:1.6,10:1.7,10:1.8,10:1.9 or 10:2.
In above-mentioned preparation method, in step (1), the temperature of described reaction can be 150～250 ℃, specifically can be 150 ℃, 200 ℃ or 250 ℃, pressure can be 0.5～2MPa, specifically can be 0.5～1.5MPa, 0.5MPa, 1.0MPa, 1.5MPa or 2MPa, the time is 12～36h, specifically can be 12～24h, 12h, 16h, 18h, 24h or 36h.
In above-mentioned preparation method, in step (2), the addition of described NaOH or potassium hydroxide can be 10%～15% of described petroleum distillate oil quality, specifically can be 10%, 12% or 15%.
In above-mentioned preparation method, in step (2), the temperature of described reaction can be 150～250 ℃, specifically can be 150 ℃, 200 ℃ or 250 ℃, and the time can be 1～2h, specifically can be 2h.
In above-mentioned preparation method, in step (2), after described reaction was complete, described method also comprises carried out cooling step with described upgrading viscosity reduction catalyst.
In above-mentioned preparation method, described cooling temperature can be 50～90 ℃, specifically can be 50 ℃, 60 ℃, 70 ℃ or 90 ℃.
The present invention also further provides the upgrading viscosity reduction that is prepared by said method catalyst, and upgrading viscosity reduction catalyst of the present invention has heat-resistant salt-resistant performance, universality preferably, and low price.
The present invention has following beneficial effect:
(1) preparation method of the present invention includes only two steps of oxidation-saponification: the oxidation technology of petroleum distillate and modifying catalyst preparation technology are organically combined, greatly reduced intermediate link and follow-up separation process;
(2) preparation method of the present invention, utilize the air oxidation of transition metal salt catalysis petroleum distillate to generate petroleum carboxylate, and transition metal salt is at first as the oxidation catalyst of petroleum distillate; Generate the hydroxide of transition metal after adding NaOH, then with the oil carboxylic acid reaction, generate upgrading viscosity reduction catalyst, transition metal salt is again the reactant of target product (catalyst) simultaneously; Therefore do not need to add extra catalyst in preparation method of the present invention, the aliphatic acid that oxidation generates does not need to separate with unoxidized distillate yet, and unoxidized distillate directly can be used as the solvent of catalyst;
(3) only need to add a material (alkali) in preparation method of the present invention, and production process operates under identical temperature, pressure, technical process is simple, can continued operation, easily control, and all be better than present method for preparing catalyst on technique and cost;
(4) preparation method of the present invention, utilize fraction oil of petroleum as raw material, wherein not only contain the alkyl of long-chain, also contain a large amount of alkyl aromatics, the alkyl carboxylate is not only arranged in the product that obtains, also have a large amount of aromatic carboxylic-acid salts, therefore, the catalyst heat-resistant salt-resistant performance for preparing is better;
(5) preparation method's of the present invention raw material sources are in oil, therefore good with the viscous crude intermiscibility, and have good universality; Synthesis material (petroleum distillate and air) wide material sources, catalytic activity is high, and production technology is simple, and low price is having good applicability and wide market prospects aspect the raising thick oil recovery ratio.
The specific embodiment
The experimental technique that uses in following embodiment if no special instructions, is conventional method.
In following embodiment, material used, reagent etc., if no special instructions, all can obtain from commercial channels.
Embodiment 1, preparation 1# catalyst
Add 100g kerosene and 15g Fe in reactor
2(SO
4)
3, be under the condition of 0.5MPa at 200 ℃, air pressure, reacted 36 hours; Add 10g NaOH after reacting completely, continue reaction 2h, be cooled to 50 ℃ of dischargings, obtain the modifying catalyst product (1# catalyst) of paste.
Embodiment 2, preparation 2# catalyst
Add 100g diesel oil and 20g CuSO in reactor
4, be under the condition of 2MPa at 150 ℃, air pressure, reacted 24 hours; Add 10g potassium hydroxide after reacting completely, continue reaction 2h, be cooled to 70 ℃ of dischargings, obtain the modifying catalyst product (2# catalyst) of paste.
Embodiment 3, preparation 3# catalyst
Add 50g diesel oil, 50g kerosene and 16g CuSO in reactor
4, be under the condition of 1.5MPa at 250 ℃, air pressure, reacted 12 hours; Add 15g NaOH after reacting completely, continue reaction 2h, be cooled to 90 ℃ of dischargings, obtain the modifying catalyst product (3# catalyst) of paste.
Embodiment 4, preparation 4# catalyst
(boiling range is 210～340 ℃, density 0.7848g/cm to add 100g vacuum 1st side cut distillate in reactor
3) and 19g MnCl
2, be under the condition of 1MPa at 150 ℃, air pressure, reacted 24 hours; Add 10g NaOH after reacting completely, continue reaction 2h, be cooled to 50 ℃ of dischargings, obtain the modifying catalyst product (4# catalyst) of paste.
Embodiment 5, preparation 5# catalyst
(boiling range is 360～430 ℃, density 0.9145g/cm to add 100g to subtract three line distillates in reactor
3) and 18g NiSO
4, be under the condition of 1.5MPa at 150 ℃, air pressure, reacted 36 hours; Add 10g NaOH after reacting completely, continue reaction 2h, be cooled to 70 ℃ of dischargings, obtain the modifying catalyst product (5# catalyst) of paste.
Embodiment 6, preparation 6# catalyst
(boiling range is 420～500 ℃, density 0.9335g/cm to add 100g to subtract four line distillates in reactor
3) and 18g ZnCl
2, be under the condition of 1.5MPa at 200 ℃, air pressure, reacted 24 hours; Add 10g NaOH after reacting completely, continue reaction 2h, be cooled to 50 ℃ of dischargings, obtain the modifying catalyst product (6# catalyst) of paste.
Embodiment 7, preparation 7# catalyst
(boiling range is 210～340 ℃, density 0.7848g/cm to add 50g vacuum 1st side cut distillate in reactor
3), (boiling range is 280～360 ℃ to the 50g Light lube oil, density 0.8051g/cm
3) and 18g ZnCl
2, be under the condition of 1.5MPa at 200 ℃, air pressure, reacted 24 hours; Add 10g potassium hydroxide after reacting completely, continue reaction 2h, be cooled to 50 ℃ of dischargings, obtain the modifying catalyst product (7# catalyst) of paste.
Embodiment 8, preparation 8# catalyst
Add 100g diesel oil, 10g CuSO in reactor
4With 6g FeCl
3, be under the condition of 1.5MPa at 200 ℃, air pressure, reacted 18 hours; Add 12g NaOH after reacting completely, continue reaction 2h, be cooled to 60 ℃ of dischargings, obtain the modifying catalyst product (8# catalyst) of paste.
Embodiment 9, preparation 9# catalyst
(boiling range is 210～340 ℃, density 0.7848g/cm to add 30g diesel oil, 30g kerosene, 40g vacuum 1st side cut distillate in reactor
3), 16g FeCl
3, be under the condition of 1MPa at 200 ℃, air pressure, reacted 24 hours; Add 15g NaOH after reacting completely, continue reaction 2h, be cooled to 80 ℃ of dischargings, obtain the modifying catalyst product (9# catalyst) of paste.
Embodiment 10, preparation 10# catalyst
Add 100g diesel oil, g CuSO in reactor
4, 6g FeCl
3With 6g NiSO
4, be under the condition of 1.5MPa at 200 ℃, air pressure, reacted 16 hours; Add 10g NaOH after reacting completely, continue reaction 2h, be cooled to 50 ℃ of dischargings, obtain the modifying catalyst product (10# catalyst) of paste.
The application of embodiment 11,1#～10# catalyst
Catalyst prod obtained above is applied to respectively different upgrading viscosity reduction experiments.
1#～10# catalyst, formation water and viscous crude are placed in autoclave, and take the quality of oil as benchmark, the consumption of upgrading thinner is the 0.1%(mass percent), amount of water is the 30%(mass percent), carry out upgrading 120h under 240 ℃ of conditions.Upgrading viscosity reducing effect such as table 1.
The viscosity reducing effect of table 1 different catalysts
Data from table 1 can find out, the down-hole upgrading viscosity reduction catalyst for preparing by the present invention all has good catalytic viscosity reduction effect, and viscosity break ratio, all more than 75%, illustrate that catalyst activity of the present invention is high, and viscosity reducing effect is good.
Claims (10)
1. the preparation method of a upgrading viscosity reduction catalyst, comprise the steps:
(1) in air atmosphere, fraction oil of petroleum and transition metal inorganic salts react;
(2) after reacting completely described in step (1),, to adding in the reaction system of described reaction NaOH or potassium hydroxide to continue reaction, react after complete and namely obtain described upgrading viscosity reduction catalyst.
2. preparation method according to claim 1, it is characterized in that: described fraction oil of petroleum is kerosene, diesel oil, vacuum 1st side cut distillate, Light lube oil, subtracts three line distillates and subtract in four line distillates at least a.
3. preparation method according to claim 1 and 2, it is characterized in that: described transition metal inorganic salts are at least a in ferric sulfate, manganese sulfate, zinc sulfate, copper sulphate, cobaltous sulfate, vanadic sulfate, molybdenum trisulfate and nickelous sulfate.
4. the described preparation method of any one according to claim 1-3, it is characterized in that: in step (1), described fraction oil of petroleum and described transition metal inorganic salts mass ratio are 10:1～2.
5. the described preparation method of any one according to claim 1-4, it is characterized in that: in step (1), the temperature of described reaction is 150～250 ℃, and pressure is 0.5～2MPa, and the time is 12～36h.
6. the described preparation method of any one according to claim 1-5, it is characterized in that: in step (2), the addition of described NaOH or potassium hydroxide is 10%～15% of described petroleum distillate oil quality.
7. the described preparation method of any one according to claim 1-6, it is characterized in that: in step (2), the temperature of described reaction is 150～250 ℃, and the time is 1～2h.
8. the described preparation method of any one according to claim 1-6, it is characterized in that: in step (2), after described reaction was complete, described method also comprises carried out cooling step with described upgrading viscosity reduction catalyst.
9. preparation method according to claim 8, it is characterized in that: described cooling temperature is 50～90 ℃.
10. the upgrading viscosity reduction catalyst that in claim 1-9, the described method of any one prepares.
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| CN106089167A (en) * | 2016-06-23 | 2016-11-09 | 中国石油天然气股份有限公司 | The method that a kind of viscous crude underground catalytic modification fall is glutinous |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee after: CNOOC research institute limited liability company Patentee after: China Offshore Oil Group Co., Ltd. Co-patentee after: Southwest Petroleum University Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee before: CNOOC Research Institute Patentee before: China National Offshore Oil Corporation Co-patentee before: Southwest Petroleum University |
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Effective date of registration: 20191211 Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee after: CNOOC research institute limited liability company Patentee after: China Offshore Oil Group Co., Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee before: CNOOC research institute limited liability company Patentee before: China Offshore Oil Group Co., Ltd. Co-patentee before: Southwest Petroleum University |