CN105733657B - A kind of demetallated method of hydrocarbon oil metal removal agent and hydrocarbon ils - Google Patents
A kind of demetallated method of hydrocarbon oil metal removal agent and hydrocarbon ils Download PDFInfo
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- CN105733657B CN105733657B CN201410753428.3A CN201410753428A CN105733657B CN 105733657 B CN105733657 B CN 105733657B CN 201410753428 A CN201410753428 A CN 201410753428A CN 105733657 B CN105733657 B CN 105733657B
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Abstract
A kind of demetallated method of hydrocarbon oil metal removal agent and hydrocarbon ils, the hydrocarbon oil metal removal agent is ketone acid, the ketone acid is any one in α ketone acids, β ketone acids, γ ketone acids, and the α ketone acids are one kind in pyruvic acid, 2 batanone acids, phenylpyruvic acid, benzoyl formic acid；The β ketone acids are acetoacetate；The γ ketone acids are 4 oxopentanoic acids.Hydrocarbon ils, water, metal remover, demulsifier are mixed and contacted, then realized water-oil separating by electro-desalting and remove the metal in hydrocarbon ils using ketone acid as metal remover by methods described.The metal remover molecule of the present invention contains difunctional, can occur chelation with metal, can occur complexing with metal again, so as to have high removal efficiency to the metal in hydrocarbon ils, metal remover acidity is between organic acid and inorganic acid, and its corrosivity is weaker than inorganic acid, but metal removal speed ratio organic acid is big, the metal remover does not contain the elements such as phosphorus, sulphur, nitrogen simultaneously, and following process will not be adversely affected.
Description
Technical field
The present invention relates to hydrocarbon oil refining agent, specifically a kind of hydrocarbon oil metal removal agent and its Demetalization method by hydrocarbon oil.
Background technology
With the progress and the intensification of oil extraction degree of exploitation technology, the crude oil of a large amount of high metal contents is continuous
Ground is mined, the presence of higher metal pollutant in crude oil, largely limits the further raising of working depth,
In hydrocracking process, metal can make rapid catalyst deactivation or fouling, and easily be deposited between catalyst granules, especially
It causes the pressure drop of hydrogenation reactor to raise rapidly at the top of fixed bed, causes device not run normally；Split in catalysis
During change, metal deposit limits hydrocarbon molecule and contacted with catalyst on the surface of catalyst, or even makes catalyst poisoning and forever
Inactivate long；For delay coking process, metal can turn into ash content in petroleum coke, influence the quality problems of petroleum coke；Metal can also
Heat transmission equipment structure is caused, causes heat-transfer effect to be deteriorated, therefore the solution of viscous crude demetalization problem is very necessary and urgent.
At present, in the demetalization technology developed both at home and abroad, chelate precipitation need not change existing technology of electric de-salting,
It is widely used in refinery.Chelate precipitation is that chelating agent or precipitating reagent are injected into electric desalting apparatus together with hydrocarbon ils
In, metal remover is reacted with the metallic compound in hydrocarbon ils, demetallated purpose is reached while desalting and dewatering, because
This selects efficient metal remover most important in chelate precipitation.The chelating agent that existing literature and Patents are used is main
There are inorganic acid, organic acid and its salt, organic acid and its salt are included：Amino acid or its esters, dicarboxylic acids or its esters, unitary carboxylic
Acid or its esters, hydroxycarboxylic acid or its esters, organic phospho acid or its esters, such as US498843, CN031371175 are with monocarboxylic acid
For metal remover, CN89102016, US4853109 using dicarboxylic acids as metal remover, CN87105863, US4789463,
US4778592 using hydroxycarboxylic acid as metal remover, CN86107286 using amino carboxylic acid as metal remover, CN97122088,
CN98117505 is using organic phospho acid as metal remover.Above-mentioned metal remover has certain removal effect to metals such as calcium, magnesium, iron,
But there is also some problems：(1) inorganic acid corrosivity is strong；(2) organic acid and its salt metal removal rate are low；(3) metal remover
Containing elements such as sulphur, phosphorus, nitrogen, follow-up secondary operation can be adversely affected.CN1295303C discloses a kind of de- gold of hydrocarbon ils
Category method, using acetylacetone,2,4-pentanedione as metal remover, with the metal in hydrocarbon ils complexing occurs for acetylacetone,2,4-pentanedione, so as to remove hydrocarbon ils
In metal.But it is due to that acetylacetone,2,4-pentanedione has Precipitation during decalcification, causes device pipeline scaling to block.
The content of the invention
To achieve the above object, the present invention provides a kind of hydrocarbon oil metal removal agent and the demetallated method of hydrocarbon ils, existing to solve
There is the defect of metal remover.
To achieve the above object, the present invention proposes a kind of hydrocarbon oil metal removal agent, and the hydrocarbon oil metal removal agent is ketone acid, described
Ketone acid is any one or its combination in 2-ketoacid, beta-keto acid or γ -one acid, the 2-ketoacid be pyruvic acid, 2- batanone acids,
One kind or its combination in phenylpyruvic acid, benzoyl formic acid；The beta-keto acid is acetoacetate；The γ -one acid is 4- pentanones
Acid.
Moreover, to achieve the above object, the present invention provides a kind of demetallated method of hydrocarbon ils, and demetalization is used as using ketone acid
Agent, hydrocarbon ils, water, metal remover, demulsifier are mixed and contacted, then water-oil separating is realized by electro-desalting and removes in hydrocarbon ils
Metal, the ketone acid is any one or its combination in 2-ketoacid, beta-keto acid or γ -one acid, the 2-ketoacid be pyruvic acid,
One kind or its combination in 2- batanone acids, phenylpyruvic acid, benzoyl formic acid；The beta-keto acid is acetoacetate；The γ -one acid
For 4- oxopentanoic acids.
Wherein, the mole dosage of the metal remover be hydrocarbon ils in calcium, magnesium, 2-8 times of iron total moles consumption, be preferably
2.5-5 again.
Wherein, the demulsifier is commercially available demulsifier, and its consumption is the 20-200 μ g/g of hydrocarbon ils weight.
Wherein, water injection rate is the 3%-10% of hydrocarbon ils weight.
Wherein, the mixing temperature of hydrocarbon ils and water, metal remover, demulsifier is 60-100 DEG C.
Wherein, the electro-desalting condition：Desalination temperature is 120-135 DEG C, 300-600v/cm weak electric fields 5-10min, 900-
It is dehydrated under the conditions of 1500v/cm highfields 10-30min.
Wherein, methods described decalcification rate reaches 80-90%, and the removal efficiency of magnesium and iron reaches 60-70%.
Innovative proposing of the invention uses ketone acid, especially pyruvic acid, 2- batanone acids, phenylpyruvic acid, benzoyl first
Acid, acetoacetate, 4- oxopentanoic acids are hydrocarbon oil metal removal agent, and ketone acid metal remover molecule proposed by the present invention contains difunctional,
Can occur chelation with metal, can occur complexing with metal again, so as to have high removing to the metal in hydrocarbon ils
Rate, metal remover acidity is between organic acid and inorganic acid, and its corrosivity is weaker than inorganic acid, but metal removal speed ratio has
Machine acid is big, while the metal remover does not contain the elements such as phosphorus, sulphur, nitrogen, following process will not be adversely affected.
Embodiment
The present invention proposes a kind of hydrocarbon oil metal removal agent, and the hydrocarbon oil metal removal agent is ketone acid, the ketone acid be 2-ketoacid, β-
Any one in ketone acid, γ -one acid or its combination, the 2-ketoacid is pyruvic acid, 2- batanone acids, phenylpyruvic acid, benzoyl
One kind or its combination in formic acid；The beta-keto acid is acetoacetate；The γ -one acid is 4- oxopentanoic acids.
Moreover, the present invention provides a kind of demetallated method of hydrocarbon ils, using ketone acid as metal remover, by hydrocarbon ils, water, de- gold
Belong to agent, demulsifier mixing contact, water-oil separating is then realized by electro-desalting and the metal in hydrocarbon ils is removed, the ketone acid be α-
Ketone acid, beta-keto acid, γ -one acid in any one, the 2-ketoacid be pyruvic acid, 2- batanone acids, phenylpyruvic acid, benzoyl first
One kind in acid；The beta-keto acid is acetoacetate；The γ -one acid is 4- oxopentanoic acids.
Specifically, the present invention proposes a kind of hydrocarbon oil metal removal agent, using ketone acid as metal remover, by hydrocarbon ils, water, de- gold
Category agent, demulsifier are sufficiently mixed contact, then realize that water-oil separating removes the metal in hydrocarbon ils by electric field.
The ketone acid is any one in 2-ketoacid, beta-keto acid, γ -one acid.
The 2-ketoacid is one kind in pyruvic acid, 2- batanone acids, phenylpyruvic acid, benzoyl formic acid；Beta-keto acid is acetyl
Acetic acid；γ -one acid is 4- oxopentanoic acids.
The mole dosage of the metal remover be hydrocarbon ils in calcium, magnesium, 2-8 times of iron total moles consumption.
The mole dosage of the metal remover be hydrocarbon ils in calcium, magnesium, 2.5-5 times of iron total moles consumption.
The demulsifier is energy oil-water separation, the commercially available general de-emulsifier being fully demulsified, and its consumption is the 20- of hydrocarbon ils weight
200μg/g。
The water injection rate is the 3%-10% of hydrocarbon ils weight.
The mixing temperature of the hydrocarbon ils and water, metal remover, demulsifier is 60-100 DEG C.
The process for demetalizating is sufficiently mixed with water, metal remover, demulsifier for hydrocarbon ils and contacted, then de- using conventional electricity
Salt realizes water-oil separating and removes the metal in hydrocarbon ils, and conventional Process Conditions for Electrostatic Desalting is：120-135 DEG C of desalination temperature, 300-
600v/cm weak electric field 5-10min, 900-1500v/cm highfields 10-30min.
Metal remover in the present invention has good removal effect to the calcium in hydrocarbon ils, magnesium, iron, and hydrocarbon ils is de- through metal remover
After metal, decalcification rate can reach 80-90%, and the removal efficiency of magnesium and iron can reach 60-70%.
Embodiment
The present invention is not limited by following embodiments, and tool can be determined according to technical scheme and actual conditions
The embodiment of body.
Metal remover is commercially available prod, and KR-40 is produced by Karamay City Jinshan Petrochemical Co., Ltd, OX-2 by gram
La Mayi Losecs company is produced, and boxshear apparatus is produced by Shanghai Wei Yu companies, takes off the assay method reference of metal ion in rear crude oil
《Petrochemical Engineering Analysis method》In 124-90 methods.
Embodiment 1
Hydrocarbon ils：Calcium content is 230 μ g/g, and content of magnesium is 2.87 μ g/g, and iron content is 14.5 μ g/g；Metal remover：Acetone
Acid, in an amount of from calcium in hydrocarbon ils, magnesium, 2.0 times of iron total moles consumption；Demulsifier：KR-40,200 μ g/g of hydrocarbon ils weight；Electricity is de-
Salt water filling：7%；Metal remover, demulsifier, electro-desalting water filling and hydrocarbon ils are sufficiently mixed at 90 DEG C with emulsification boxshear apparatus shearing,
It is placed in electric desalting apparatus, under the conditions of 120 DEG C of desalination temperatures, 600v/cm weak electric field 10min, 1000v/cm highfields 20min
Dehydration, after water-oil separating, the oily tenor/demetallization per of analysis purification, calcium content/decalcification rate：45.8 μ g/g/80.1%, magnesium
Content/demagnesium rate：1.15 μ g/g/60.0%, iron content/deferrization rate：5.7 μ g/g/60.5%.
Embodiment 2
Hydrocarbon ils：Calcium content is 38.5 μ g/g, and content of magnesium is 1.85 μ g/g, and iron content is 4.3 μ g/g；Metal remover：Acetone
Acid, in an amount of from calcium in hydrocarbon ils, magnesium, 5.0 times of iron total moles consumption；Demulsifier：OX-2,100 μ g/g of hydrocarbon ils weight.；Electricity is de-
Salt water filling：10%；Metal remover, demulsifier, electro-desalting water filling and hydrocarbon ils are sufficiently mixed at 80 DEG C with emulsification boxshear apparatus shearing,
It is placed in electric desalting apparatus, is taken off under the conditions of 135 DEG C of desalination temperatures, 300v/cm weak electric field 5min, 900v/cm highfields 30min
Water, after water-oil separating, the oily tenor/demetallization per of analysis purification, calcium content/decalcification rate：4.6 μ g/g/88.1%, magnesium contains
Amount/demagnesium rate：0.57 μ g/g/69.2%, iron content/deferrization rate：1.44 μ g/g/66.5%.
Embodiment 3
Hydrocarbon ils：Calcium content is 721 μ g/g, and content of magnesium is 5.25 μ g/g, and iron content is 16.7 μ g/g；Metal remover：Acetyl
Acetic acid, in an amount of from calcium in hydrocarbon ils, magnesium, 8.0 times of iron total moles consumption；Demulsifier：OX-2,150 μ g/g.；Electro-desalting water filling：
7%；Metal remover, demulsifier, electro-desalting water filling and hydrocarbon ils are sufficiently mixed at 60 DEG C with emulsification boxshear apparatus shearing, electricity is placed in de-
In salt device, it is dehydrated under the conditions of 130 DEG C of desalination temperatures, 500v/cm weak electric field 8min, 1500v/cm highfields 10min, profit
After separation, the oily tenor/demetallization per of analysis purification, calcium content/decalcification rate：87.2 μ g/g/87.9%, content of magnesium/de-magging
Rate：1.66 μ g/g/68.3%, iron content/deferrization rate：5.5 μ g/g/67.1%.
Embodiment 4
Hydrocarbon ils：Calcium content is 180 μ g/g, and content of magnesium is 12.5 μ g/g, and iron content is 41.5 μ g/g；Metal remover：Acetone
Acid, in an amount of from calcium in hydrocarbon ils, magnesium, 2.5 times of iron total moles consumption；Demulsifier：OX-2,20 μ g/g.；Electro-desalting water filling：3%；
Metal remover, demulsifier, electro-desalting water filling and hydrocarbon ils are sufficiently mixed at 90 DEG C with emulsification boxshear apparatus shearing, electro-desalting dress is placed in
In putting, it is dehydrated under the conditions of 120 DEG C of desalination temperatures, 400v/cm weak electric field 7min, 1000v/cm highfields 15min, water-oil separating
Afterwards, the oily tenor/demetallization per of analysis purification, calcium content/decalcification rate：32.0 μ g/g/82.2%, content of magnesium/demagnesium rate：
4.8 μ g/g/61.6%, iron content/deferrization rate：15.1 μ g/g/63.5%.
Embodiment 5
Hydrocarbon ils：Calcium content is 230 μ g/g, and content of magnesium is 2.87 μ g/g, and iron content is 14.5 μ g/g；Metal remover：2- fourths
Ketone acid, in an amount of from calcium in hydrocarbon ils, magnesium, 5.0 times of iron total moles consumption；Demulsifier：KR-41,100 μ g/g.；Electro-desalting water filling：
6%；Metal remover, demulsifier, electro-desalting water filling and hydrocarbon ils are sufficiently mixed at 60 DEG C with emulsification boxshear apparatus shearing, electricity is placed in de-
In salt device, it is dehydrated under the conditions of 125 DEG C of desalination temperatures, 600v/cm weak electric field 10min, 1000v/cm highfields 20min, oil
After water separation, the oily tenor/demetallization per of analysis purification, calcium content/decalcification rate：43.5 μ g/g/81.1%, content of magnesium/de-
Magnesium rate：1.02 μ g/g/64.4%, iron content/deferrization rate：5.8 μ g/g/60.0%.
Embodiment 6
Hydrocarbon ils：Calcium content is 230 μ g/g, and content of magnesium is 2.87 μ g/g, and iron content is 14.5 μ g/g；Metal remover：Phenylpropyl alcohol
Ketone acid, in an amount of from calcium in hydrocarbon ils, magnesium, 5.0 times of iron total moles consumption；Demulsifier：KR-41,150 μ g/g.；Electro-desalting water filling：
8%；Metal remover, demulsifier, electro-desalting water filling and hydrocarbon ils are sufficiently mixed at 60 DEG C with emulsification boxshear apparatus shearing, electricity is placed in de-
In salt device, it is dehydrated under the conditions of 130 DEG C of desalination temperatures, 600v/cm weak electric field 6min, 1000v/cm highfields 20min, profit
After separation, the oily tenor/demetallization per of analysis purification, calcium content/decalcification rate：41.2 μ g/g/82.1%, content of magnesium/de-magging
Rate：0.97 μ g/g/66.3%, iron content/deferrization rate：5.5 μ g/g/61.9%.
Embodiment 7
Hydrocarbon ils：Calcium content is 721 μ g/g, and content of magnesium is 5.25 μ g/g, and iron content is 16.7 μ g/g；Metal remover：Benzene first
Ethyl acetoacetic acid, in an amount of from calcium in hydrocarbon ils, magnesium, 6.0 times of iron total moles consumption；Demulsifier：OX-2,100 μ g/g.；Electro-desalting water filling：
8%；Metal remover, demulsifier, electro-desalting water filling and hydrocarbon ils are sufficiently mixed at 80 DEG C with emulsification boxshear apparatus shearing, electricity is placed in de-
In salt device, it is dehydrated under the conditions of 120 DEG C of desalination temperatures, 600v/cm weak electric field 10min, 1000v/cm highfields 20min, oil
After water separation, the oily tenor/demetallization per of analysis purification, calcium content/decalcification rate：93.0 μ g/g/87.1%, content of magnesium/de-
Magnesium rate：1.68 μ g/g/68.0%, iron content/deferrization rate：5.6 μ g/g/66.5%.
Embodiment 8
Hydrocarbon ils：Calcium content is 38.5 μ g/g, and content of magnesium is 1.85 μ g/g, and iron content is 4.3 μ g/g；Metal remover：4- penta
Ketone acid, in an amount of from calcium in hydrocarbon ils, magnesium, 7.0 times of iron total moles consumption；Demulsifier：OX-2,150 μ g/g.；Electro-desalting water filling：
7%；Metal remover, demulsifier, electro-desalting water filling and hydrocarbon ils are sufficiently mixed at 60 DEG C with emulsification boxshear apparatus shearing, electricity is placed in de-
In salt device, it is dehydrated under the conditions of 120 DEG C of desalination temperatures, 600v/cm weak electric field 10min, 1000v/cm highfields 20min, oil
After water separation, the oily tenor/demetallization per of analysis purification, calcium content/decalcification rate：7.7 μ g/g/79.9%, content of magnesium/de-magging
Rate：0.73 μ g/g/60.4%, iron content/deferrization rate：1.63 μ g/g/62.1%.
Embodiment 9
Hydrocarbon ils：Calcium content is 230 μ g/g, and content of magnesium is 2.87 μ g/g, and iron content is 14.5 μ g/g；Metal remover：Acetone
Acid, in an amount of from 5.0 times of metals in hydrocarbon oil total moles consumption；Demulsifier：KR-41,100 μ g/g.；Electro-desalting water filling：7%；Will
Metal remover, demulsifier, electro-desalting water filling and hydrocarbon ils are sufficiently mixed at 100 DEG C with emulsification boxshear apparatus shearing, are placed in electro-desalting dress
In putting, it is dehydrated under the conditions of 120 DEG C of desalination temperatures, 600v/cm weak electric field 9min, 1200v/cm highfields 25min, water-oil separating
Afterwards, the oily tenor/demetallization per of analysis purification, calcium content/decalcification rate：20.7 μ g/g/91.0%, content of magnesium/demagnesium rate：
0.87 μ g/g69.5%, iron content/deferrization rate：4.3 μ g/g/70.1%.
Innovative proposing of the invention uses ketone acid, especially pyruvic acid, 2- batanone acids, phenylpyruvic acid, benzoyl first
Acid, acetoacetate, 4- oxopentanoic acids are hydrocarbon oil metal removal agent, and the metal remover molecule contains difunctional, can occurred with metal
Chelation, can occur complexing, so as to have high removal efficiency to the metal in hydrocarbon ils, its decalcification rate is reachable with metal again
To 80-90%, the removal efficiency of magnesium and iron can reach 60-70%.Also, ketone acid metal remover proposed by the present invention is acid between having
Between machine acid and inorganic acid, its corrosivity is weaker than inorganic acid, but metal removal speed ratio organic acid is big, while the metal remover is not
Containing elements such as phosphorus, sulphur, nitrogen, following process will not be adversely affected.
Also, the present invention Demetalization method by hydrocarbon oil in using pyruvic acid, 2- batanone acids, phenylpyruvic acid, benzoyl formic acid,
Acetoacetate, 4- oxopentanoic acids are as hydrocarbon oil metal removal agent, and the mole dosage of metal remover is calcium, magnesium, iron total moles in hydrocarbon ils
In particular 2.5-5 times of 2-8 times of consumption, promotes chelation and complexing that metal remover occurs with metal, further
Improve the extrusion rate of metal.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (9)
1. application of a kind of ketone acid in hydrocarbon oil metal removal agent, it is characterised in that the hydrocarbon oil metal removal agent is ketone acid, the ketone
Acid is 2-ketoacid, any one or its combination in beta-keto acid, γ -one acid, and the 2-ketoacid is pyruvic acid, 2- batanone acids, benzene
One kind or its combination in pyruvic acid, benzoyl formic acid；The beta-keto acid is acetoacetate；The γ -one acid is 4- oxopentanoic acids.
2. a kind of demetallated method of hydrocarbon ils, it is characterised in that using ketone acid as metal remover, by hydrocarbon ils, water, metal remover,
Demulsifier mixing contact, water-oil separating is then realized by electro-desalting and the metal in hydrocarbon ils is removed, the ketone acid be 2-ketoacid,
Beta-keto acid, γ -one acid in any one, the 2-ketoacid be pyruvic acid, 2- batanone acids, phenylpyruvic acid, benzoyl formic acid in
One kind；The beta-keto acid is acetoacetate；The γ -one acid is 4- oxopentanoic acids.
3. method according to claim 2, it is characterised in that the mole dosage of the metal remover be calcium in hydrocarbon ils, magnesium,
2-8 times of iron total moles consumption.
4. method according to claim 3, it is characterised in that the mole dosage of the metal remover be calcium in hydrocarbon ils, magnesium,
2.5-5 times of iron total moles consumption.
5. method according to claim 2, it is characterised in that the demulsifier is commercially available demulsifier, its consumption is hydrocarbon ils
The 20-200 μ g/g of weight.
6. method according to claim 2, it is characterised in that water injection rate is the 3%-10% of hydrocarbon ils weight.
7. method according to claim 2, it is characterised in that the mixing temperature of hydrocarbon ils and water, metal remover, demulsifier is
60-100℃。
8. method according to claim 2, it is characterised in that the electro-desalting condition：Desalination temperature be 120-135 DEG C,
300-600v/cm weak electric field 5-10min, 900-1500v/cm highfields 10-30min.
9. method according to claim 2, it is characterised in that methods described decalcification rate reaches 80-90%, magnesium and iron it is de-
Except rate reaches 60-70%.
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| CN106381166A (en) * | 2016-10-21 | 2017-02-08 | 中国海洋石油总公司 | Method for decalcifying crude oil by ketonic acid |
| CN108707470B (en) * | 2018-06-14 | 2021-05-04 | 陕西省石油化工研究设计院 | Oil demetallization agent and preparation method and application thereof |
| CN109609178B (en) * | 2018-12-19 | 2021-07-16 | 克拉玛依新科澳石油天然气技术股份有限公司 | Demulsifier for treating thick oil and preparation method thereof |
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| CN1120575A (en) * | 1994-10-14 | 1996-04-17 | 王中亭 | Removal of metal from oil with organic phospho acid and its salt |
| CN1693424A (en) * | 2005-06-01 | 2005-11-09 | 华东理工大学 | Process for demetalizating of hydrocarbon oil |
| CN101067012A (en) * | 2007-05-22 | 2007-11-07 | 华东理工大学 | Application of copolymer of acrylic acid (acrylate), acrylic anhydride and amide in demetallizing hydrocarbon oil |
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| CN86107286A (en) * | 1985-10-30 | 1987-09-16 | 切夫昂研究公司 | The method that adopts aminocarboxylic acid and salt pair hydrocarbon raw material to carry out decalcification |
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| CN1036981A (en) * | 1988-03-07 | 1989-11-08 | 切夫尔昂研究公司 | From hydrocarbon feed, remove metal with di-carboxylic acid and its esters |
| US4988433A (en) * | 1988-08-31 | 1991-01-29 | Chevron Research Company | Demetalation of hydrocarbonaceous feedstocks using monobasic carboxylic acids and salts thereof |
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Effective date of registration: 20180711 Address after: 100007 Oil Mansion, Oil Mansion, 9 Dongzhimen North Street, Dongcheng District, Beijing. Co-patentee after: PetroChina Karamay Petrochemical Co., Ltd. Patentee after: China Petroleum & Natural Gas Co., Ltd. Address before: 100007 Oil Mansion, Oil Mansion, 9 Dongzhimen North Street, Dongcheng District, Beijing. Patentee before: China Petroleum & Natural Gas Co., Ltd. |
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