CN114933914A - Catalytic cracking external-throwing slurry oil deliming agent and preparation method thereof - Google Patents
Catalytic cracking external-throwing slurry oil deliming agent and preparation method thereof Download PDFInfo
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- CN114933914A CN114933914A CN202210465190.9A CN202210465190A CN114933914A CN 114933914 A CN114933914 A CN 114933914A CN 202210465190 A CN202210465190 A CN 202210465190A CN 114933914 A CN114933914 A CN 114933914A
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- oil
- polyether
- catalytic cracking
- slurry
- agent
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- 239000002002 slurry Substances 0.000 title claims abstract description 47
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 65
- 229920000570 polyether Polymers 0.000 claims abstract description 65
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- 229920001577 copolymer Polymers 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 20
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000003999 initiator Substances 0.000 claims description 21
- 239000012986 chain transfer agent Substances 0.000 claims description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 8
- 239000011976 maleic acid Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 claims description 5
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical group C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000003921 oil Substances 0.000 description 50
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 22
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 21
- 238000005227 gel permeation chromatography Methods 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000011049 filling Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- -1 polyoxyethylene Polymers 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/22—Organic compounds not containing metal atoms containing oxygen as the only hetero atom
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/208—Sediments, e.g. bottom sediment and water or BSW
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a catalytic cracking external throwing slurry deashing agent and a preparation method thereof, wherein the catalytic cracking external throwing slurry deashing agent comprises 5-20 omega t% of copolymer of olefine acid and allyl alcohol polyether, 10-20 omega t% of oil-soluble polyether and 60-85 omega t% of aromatic hydrocarbon solvent oil, the number average molecular weight of the copolymer is 4000-8000, and an olefine acid monomer in the copolymer is a compound containing vinyl and carboxyl. The deliming agent has the advantages of low dosage, short settling time, simple and easily obtained raw materials and mild preparation conditions.
Description
Technical Field
The invention belongs to the technical field of petroleum refining, and particularly relates to an oil slurry deliming agent for removing catalyst particles in catalytic cracking oil slurry by external throwing and a preparation method thereof.
Background
The oil slurry is a byproduct with special properties in the catalytic cracking process, is a black or brownish black sticky substance, is a non-Newtonian fluid with poor fluidity at normal temperature, and is an unconverted hydrocarbon fraction with the boiling point of more than 350 ℃ in the catalytic cracking process. The oil slurry thrown outward contains a small amount of broken solid catalyst particles, so that deep utilization of the oil slurry is limited. Along with the increase of oil refining capacity in China, the yield of the oil slurry is increased, so that the purification and the comprehensive utilization of the catalytic cracking oil slurry have important significance.
Chinese patent CN201710186438.7 provides a formaldehyde condensation polymer of alkylphenol polyoxyethylene and a preparation method thereof, wherein a dimerization condensation polymer or a trimerization condensation polymer of alkylphenol polyvinyl ether is esterified with acid anhydride to obtain a target product, the filling amount is 300-400ppm, the settling time is 24 hours, and the settling rate reaches 92%. According to the technical scheme, reactants are difficult to obtain, the production process is complex, and adverse factors such as pollution exist, so that the possibility of production and application of the catalyst is reduced.
US patent US4539099 provides a method for removing solids from oil slurry, a phenolic resin polyether crude oil demulsifier is esterified and crosslinked by using dicarboxylic acid to obtain a target product, the filling amount is 500ppm, and the settling time is 0.3-10 days. The technical scheme has the disadvantages of complex production process of the phenolic resin polyether esterification product, pollution and the like, and is not beneficial to industrial production and the like.
Chinese patent CN113046115A provides a polycarboxylic polyether ester which is a partial esterification product of polycarboxylic acid and alkylphenol polyether, emphasizes the effect of carboxyl on settling ash, and has the outstanding advantages of low filling amount (100-200ppm), short settling time (8 hours), high deashing rate and the like, but the technical scheme also faces the disadvantages of difficult obtainment of reactants, complex production process, pollution and the like.
The technical defects are obvious, the cost of raw materials is high, the process difficulty is high, and certain pollution exists, so that a new solution is needed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a catalytic cracking external-throwing slurry deashing agent and a preparation method thereof, which can effectively overcome the defects of high raw material cost, high process difficulty and certain pollution in the prior art and have the advantages of low addition amount and short settling time.
In order to achieve the purpose, the invention provides the following technical scheme:
the catalytic cracking external throwing slurry deashing agent comprises 5-20 wt% of copolymer of olefine acid and allyl alcohol polyether, 10-20 wt% of oil-soluble polyether and 60-85 wt% of aromatic hydrocarbon solvent oil, wherein the number average molecular weight of the copolymer is 4000-8000, and the olefine acid monomer in the copolymer is a compound containing vinyl and carboxyl.
In the technical scheme of the invention, the copolymerization mode of olefine acid and allyl alcohol polyether is adopted for the first time, the carboxyl monomer with stronger water solubility is connected with the oil-soluble allyl alcohol polyether, and the copolymer with a specific molecular weight range has balanced ash adsorption and oleophilic characteristics, so that the carboxyl with stronger hydrophilicity can be well dispersed in an oil phase, and the deashing effect of the copolymer is better exerted. The oil-soluble polyether and the aromatic solvent oil in the deliming agent can prevent small molecular olefine acid monomers from rapid polymerization in the copolymerization process, the oil-soluble polyether can also well promote mutual solubility of the olefine acid monomers and allyl alcohol polyether, and the deliming agent can also play a role in eliminating electricity. The oil slurry deliming agent provided by the invention can obviously improve the sedimentation efficiency of oil slurry catalyst particles, and has the characteristics of small filling amount, short sedimentation time and high removal rate. Compared with the esterified compound in the prior art, the copolymer adopted by the product has the advantages of simple and easily obtained raw materials, mild preparation conditions, low reaction temperature and no generation of three wastes.
Interpretation of terms
In the present invention, the aromatic hydrocarbon solvent oil is a generic name of a series of solvents composed of isomers of C9 and C10 heavy aromatic hydrocarbons, and its main components are trimethylbenzene, tetramethylbenzene and isomers thereof, which are also generally referred to as high boiling point aromatic hydrocarbon solvent oil.
In the present invention, the oil-soluble polyether refers to an ether compound having a solubility characteristic comparable to that of the water-soluble polyether, and is soluble in most mineral oils and synthetic oils.
As a further improvement of the technical scheme, the oil-soluble polyether is ethylene oxide-propylene oxide diblock polyether, wherein the molar content of ethylene oxide is not more than 30%, and the oil-soluble polyether can be well dissolved in oil slurry.
As a further improvement of the technical proposal, in order to better dissolve with the copolymer and disperse in oil slurry, the number average molecular weight of the oil-soluble polyether is 1000-5000.
As a further improvement of the technical scheme, the oil-soluble polyether is prepared by taking alkylphenol or fatty alcohol as a polyether initiator. The alkylphenol and the fatty alcohol belong to compounds with better lipophilicity and are common initiators, and the lipophilicity of the oil-soluble polyether can be improved.
As a further improvement of the technical scheme, the ethylene oxide molar content in the allyl alcohol polyether is 10-30% for better dissolution in oil slurry and oil-soluble polyether.
As a further improvement of the technical scheme, in order to facilitate the control of the polymerization degree and the molecular weight of the copolymer, the number average molecular weight of the allyl alcohol polyether is 500-3000.
As a further improvement of the technical scheme, the olefine acid is one or more of acrylic acid, maleic acid, 3-butenoic acid and 4-pentenoic acid.
As a further improvement of the technical proposal, the mol ratio of the allyl alcohol polyether to the olefine acid monomer in the copolymer is 1: 5-20. The low olefine acid content affects the performance of adsorbing, complexing and removing ash of the copolymer, and the high olefine acid content affects the oil solubility of the copolymer.
The invention also discloses a preparation method of the deliming agent, which comprises the following steps:
step one, adding allyl alcohol polyether, olefine acid monomer, oil-soluble polyether, aromatic hydrocarbon solvent oil and oil-soluble initiator into a reaction kettle, heating to 70-90 ℃ under the condition of air isolation, and reacting for 90-150min, wherein the air isolation can be realized by introducing inert reaction gases such as nitrogen, gas of a zero-group element and the like.
And step two, adding a chain transfer agent into the mixed solution prepared in the step one, wherein the chain transfer agent can be common chain transfer agents such as n-butylmercaptan, n-dodecylmercaptan and the like, and carrying out heat preservation reaction at 70-90 ℃ for 120-150min to obtain the target product.
In order to inhibit the polymerization of the polymerization monomer to obtain the copolymer of the olefine acid and the allyl alcohol polyether with a specific molecular weight range, the chain transfer effect of the oil-soluble polyether and the aromatic hydrocarbon solvent oil can be fully utilized by adopting a one-pot boiling mode in the preparation process, and measures such as adding a large amount of initiator once, adding the polymerization monomer in batches or adding a chain transfer agent in advance and the like are added.
As a further improvement of the technical proposal, in order to inhibit the sudden polymerization of the polymerized monomers, a large amount of initiator is added at one time, and the amount of the initiator is 2 to 4 percent of the total molar amount of the monomers used for polymerization. In the normal radical polymerization, the initiator is generally added in an amount of 0.5-1%. The initiator can be selected from azobisisobutyronitrile, benzoyl peroxide and the like.
The prior art is referred to in the art for techniques not mentioned in the present invention.
Compared with the prior art, the invention has outstanding substantive characteristics and remarkable progress, and particularly, the deliming agent adopts the copolymer of the olefine acid and the allyl alcohol polyether, and has the advantages of simple and easily obtained raw materials, mild preparation conditions, low reaction temperature and no generation of three wastes. Furthermore, the mol content of ethylene oxide in the oil-soluble polyether and the allyl alcohol polyether is not more than 30%, the lipophilicity is improved, the dispersibility in oil slurry is easier, and the removal efficiency is improved. Furthermore, the deliming agent disclosed by the invention has the advantages of small filling amount, short settling time, high settling efficiency and the like.
Detailed Description
The technical solution of the present invention is further described in detail by the following embodiments. The compounds used in the examples are commercially available, and the techniques not specified in the examples are known in the art.
Example 1
50g of allyl alcohol polyether (molecular weight Mn is 500, EO molar weight is 10%), 28.8g of acrylic acid, 11.6g of maleic acid, 45.2g of nonylphenol diblock polyether (molecular weight Mn is 500, EO molar weight is 30%), 316.4g of 1500# aromatic hydrocarbon solvent oil and 3.5g of initiator azobisisobutyronitrile are added into a reaction kettle, nitrogen is introduced for replacement for 3 times, and the temperature is raised to 70 ℃ for reaction for 90 min. Then 0.5g of chain transfer agent n-butylmercaptan is added, and the reaction is carried out for 120min at the temperature of 70 ℃ to obtain the catalytic cracking external throwing slurry deashing agent.
The number average molecular weight of the copolymer was 4534 as measured by GPC (gel chromatography).
Example 2
100g of allyl alcohol polyether (molecular weight Mn is 1000, EO molar weight is 10%), 68.8g of 3-butenoic acid, 20g of 4-pentenoic acid, 377.6g of propylene glycol diblock polyether (molecular weight Mn is 3000, EO molar weight is 30%), 1321.6g of 1500# aromatic hydrocarbon solvent oil and 7.2g of initiator azobisisobutyronitrile are added into a reaction kettle, nitrogen is introduced for replacement for 3 times, and the temperature is increased to 80 ℃ for reaction for 150 min. Then adding 1.0g of chain transfer agent n-butyl mercaptan, and reacting for 150min at the temperature of 80 ℃ to obtain the catalytic cracking external throwing slurry deashing agent.
The number average molecular weight of the copolymer was 5286 as measured by GPC (gel chromatography).
Example 3
150g of allyl alcohol polyether (molecular weight Mn is 1500, EO molar weight is 30%), 86.4g of acrylic acid, 25.8g of 3-butenoic acid, 524.4g of propylene glycol diblock polyether (molecular weight Mn is 3000, EO molar weight is 30%), 1835.4g of 1500# aromatic hydrocarbon solvent oil and 10.0g of initiator azobisisobutyronitrile are added into a reaction kettle, nitrogen is introduced for replacement for 3 times, and the temperature is raised to 90 ℃ for reaction for 120 min. Then 0.8g of chain transfer agent n-butyl mercaptan is added, and the reaction is carried out for 150min at the temperature of 90 ℃ to obtain the catalytic cracking external throwing slurry deashing agent.
The number average molecular weight of the copolymer was 6523 as measured by GPC (gel chromatography).
Example 4
200g of allyl alcohol polyether (molecular weight Mn is 2000, EO molar weight is 20%), 115.2g of acrylic acid, 40g of 4-pentenoic acid, 473.6g of propylene glycol diblock polyether (molecular weight Mn is 3000, EO molar weight is 30%), 1539.2g of S1000 aromatic hydrocarbon solvent oil and 13.5g of initiator azobisisobutyronitrile are added into a reaction kettle, nitrogen is introduced for replacement for 3 times, and the temperature is raised to 85 ℃ for reaction for 130 min. Then adding 2.0g of chain transfer agent n-butylmercaptan, and reacting for 130min at 85 ℃ to obtain the catalytic cracking external-throwing oil slurry deliming agent.
The number average molecular weight of the copolymer was 7867 as measured by GPC (gel chromatography).
Example 5
250g of allyl alcohol polyether (molecular weight Mn is 2500, EO molar weight is 20%), 115.2g of acrylic acid, 46.4g of maleic acid, 823.2g of propylene glycol diblock polyether (molecular weight Mn is 3000, EO molar weight is 30%), 2881.2g of S1000 aromatic hydrocarbon solvent oil and 6.9g of initiator azobisisobutyronitrile are added into a reaction kettle, nitrogen is introduced for replacement for 3 times, and the temperature is raised to 85 ℃ for reaction for 130 min. Then adding 2.0g of chain transfer agent n-butylmercaptan, and reacting for 130min at 85 ℃ under heat preservation to obtain the catalytic cracking external-throwing oil slurry deliming agent.
The number average molecular weight of the copolymer was 6412 as measured by GPC (gel chromatography).
Example 6
250g of allyl alcohol polyether (molecular weight Mn is 2500, EO molar weight is 20%), 115.2g of acrylic acid, 46.4g of maleic acid, 823.2g of propylene glycol diblock polyether (molecular weight Mn is 1000, EO molar weight is 10%), 6997.2g of No. 1500 aromatic hydrocarbon solvent oil and 6.9g of initiator azobisisobutyronitrile are added into a reaction kettle, nitrogen is introduced for replacement for 3 times, and the temperature is raised to 85 ℃ for reaction for 130 min. Then adding 2.0g of chain transfer agent n-butylmercaptan, and reacting for 130min at 85 ℃ to obtain the catalytic cracking external-throwing oil slurry deliming agent.
The number average molecular weight of the copolymer was 6879 as measured by GPC (gel chromatography).
Example 7
250g of allyl alcohol polyether (molecular weight Mn is 2500, EO molar weight is 20%), 115.2g of acrylic acid, 46.4g of maleic acid, 411.6g of propylene glycol diblock polyether (molecular weight Mn is 5000, EO molar weight is 30%), 3292.8g of 1500# aromatic hydrocarbon solvent oil and 10.8g of initiator azobisisobutyronitrile are added into a reaction kettle, nitrogen is introduced for replacement for 3 times, and the temperature is raised to 85 ℃ for reaction for 130 min. Then adding 2.0g of chain transfer agent n-butylmercaptan, and reacting for 130min at 85 ℃ under heat preservation to obtain the catalytic cracking external-throwing oil slurry deliming agent.
The number average molecular weight of the copolymer was 6338 as measured by GPC (gel chromatography).
Example 8
250g of allyl alcohol polyether (molecular weight Mn is 2500, EO molar weight is 20%), 115.2g of acrylic acid, 46.4g of maleic acid, 823.2g of propylene glycol diblock polyether (molecular weight Mn is 5000, EO molar weight is 20%), 6997.2g of No. 1500 aromatic hydrocarbon solvent oil and 9.6g of initiator azobisisobutyronitrile are added into a reaction kettle, nitrogen is introduced for replacement for 3 times, and the temperature is raised to 85 ℃ for reaction for 130 min. Then adding 2.0g of chain transfer agent n-butylmercaptan, and reacting for 130min at 85 ℃ under heat preservation to obtain the catalytic cracking external-throwing oil slurry deliming agent.
The number average molecular weight of the copolymer was 6156 by GPC (gel chromatography).
Comparative example 1
200g of allyl alcohol polyether (with the molecular weight Mn of 2000 and the molar weight of EO of 20%), 115.2g of acrylic acid, 40g of 4-pentenoic acid, 473.6g of propylene glycol diblock polyether (with the molecular weight Mn of 3000 and the molar weight of EO of 30%), 1539.2g of 1500# aromatic hydrocarbon solvent oil and 3.4g of azodiisobutyronitrile serving as an initiator are added into a reaction kettle, nitrogen is introduced for replacement for 3 times, and the temperature is raised to 85 ℃ for reaction for 130 min. Adding 2.0g of chain transfer agent n-butylmercaptan, and reacting for 130min at 85 ℃ under the condition of heat preservation to obtain the catalytic cracking external-throwing oil slurry deliming agent.
The number average molecular weight of the copolymer was measured by GPC (gel chromatography) and found to be 8694.
Comparative example 2
50g of allyl alcohol polyether (molecular weight Mn is 500, EO molar weight is 10%), 28.8g of acrylic acid, 11.6g of maleic acid, 45.2g of nonyl phenol diblock polyether (molecular weight Mn is 500, EO molar weight is 30%), 316.4g of 1500# aromatic hydrocarbon solvent oil and 0.5g of initiator azobisisobutyronitrile are added into a reaction kettle, nitrogen is introduced for replacement for 3 times, and the temperature is raised to 85 ℃ for reaction for 130 min. Then 0.5g of chain transfer agent n-butyl mercaptan is added, and the reaction is carried out for 130min under the heat preservation of 85 ℃, thus obtaining the catalytic cracking external throwing slurry deashing agent.
The number average molecular weight of the copolymer was 9642 as measured by GPC (gel chromatography).
Evaluation test methods: A1L settling tank is selected, 1L of oil slurry is injected into the settling tank, the settling temperature is maintained at 90-95 ℃, and the settling time is 8 hours. After the sedimentation is finished, a proper amount of oil slurry is extracted from the position 1/5 away from the bottom of the tank and burned, and the sedimentation effect is evaluated and contrasted. The deliming agents obtained in examples 1 to 8 and comparative examples 1 to 2 were used in the sedimentation, respectively, and the blank control example was carried out without any deliming agent.
Example 9
The catalyst particle content is up to 5000ppm by selecting the external throwing slurry oil from a certain refinery in Zhejiang, the injection amount of the slurry oil deliming agent is 100ppm respectively, and the data of the settlement experiment are shown in Table 1.
Table 1 settlement experiment data table
Example 10
The catalyst particle content is up to 8000ppm by using the external throwing slurry oil of a certain refinery in Jiangsu, the injection amount of the slurry oil deliming agent is 100ppm respectively, and the data of a settlement experiment are shown in a table 2.
Table 2 settlement experiment data table
As can be seen from tables 1 and 2, the oil slurry deliming agent provided by the invention has a settling effect generally reaching more than 90% under the conditions of 100ppm of filling amount and 8 hours of settling time, so that the oil slurry deliming agent provided by the invention can be used for remarkably improving the settling efficiency of oil slurry catalyst particles, and has the characteristics of small filling amount, short settling time and high removal rate.
Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present invention and not to limit the same; although the present invention has been described in detail with reference to preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention; without departing from the spirit of the present invention, it is intended to cover all aspects of the invention as defined by the appended claims.
Claims (10)
1. The catalytic cracking external-throwing slurry deashing agent is characterized by comprising 5-20 omega t% of copolymer of olefine acid and allyl alcohol polyether, 10-20 omega t% of oil-soluble polyether and 60-85 omega t% of aromatic hydrocarbon solvent oil, wherein the number average molecular weight of the copolymer is 4000-8000, and the olefine acid monomer in the copolymer is a compound containing vinyl and carboxyl.
2. The catalytic cracking external splash slurry deliming agent as claimed in claim 1, wherein the oil soluble polyether is ethylene oxide propylene oxide diblock polyether, and the ethylene oxide molar content is not more than 30%.
3. The catalytic cracking external-throwing slurry deashing agent as claimed in claim 2, wherein the number average molecular weight of the oil-soluble polyether is 1000-5000-.
4. The catalytic cracking oil slurry deashing agent according to claim 3, wherein the oil-soluble polyether is prepared by using alkylphenol or fatty alcohol as a polyether initiator.
5. The catalytic cracking external throwing slurry deashing agent of claim 1, wherein the allyl alcohol polyether has an ethylene oxide molar content of 10-30%.
6. The catalytic cracking external throwing slurry deashing agent as claimed in claim 5, wherein the allyl alcohol polyether has a number average molecular weight of 500-3000.
7. The catalytic cracking slurry deashing agent, according to claim 1, wherein the olefinic acid monomer is one or more of acrylic acid, maleic acid, 3-butenoic acid, and 4-pentenoic acid.
8. The catalytic cracking external splash slurry deliming agent as claimed in claim 1, wherein the molar ratio of allyl alcohol polyether to olefinic acid monomer in the copolymer is 1: 5-20.
9. A method of preparing the deliming agent according to any one of claims 1 to 8, comprising the steps of:
step one, adding allyl alcohol polyether, an olefine acid monomer, oil-soluble polyether, aromatic hydrocarbon solvent oil and an oil-soluble initiator into a reaction kettle, and raising the temperature to 70-90 ℃ under the condition of isolating air to react for 90-150 min;
and step two, adding a chain transfer agent into the mixed solution prepared in the step one, and carrying out heat preservation reaction at 70-90 ℃ for 120-150min to obtain the target product.
10. The method of claim 9, wherein the amount of the initiator is 2 to 4% of the total molar amount of the monomers to be polymerized in the polymerization reaction.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4678599A (en) * | 1983-10-27 | 1987-07-07 | Th. Goldschmidt Ag | Use of copolymers of polyoxyalkylene ethers of allyl and/or methallyl alcohol and vinyl esters as demulsifiers for water-containing crude oil |
| CA2168392A1 (en) * | 1996-01-30 | 1997-07-31 | Paul R. Hart | Settling aids for solids in hydrocarbons |
| CN113046115A (en) * | 2021-03-02 | 2021-06-29 | 金浦新材料股份有限公司 | Catalytic cracking slurry oil settling agent and application thereof |
| CN114181731A (en) * | 2021-12-07 | 2022-03-15 | 中海油天津化工研究设计院有限公司 | Micelle dispersion type oil slurry settling agent and preparation method thereof |
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- 2022-04-29 CN CN202210465190.9A patent/CN114933914B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4678599A (en) * | 1983-10-27 | 1987-07-07 | Th. Goldschmidt Ag | Use of copolymers of polyoxyalkylene ethers of allyl and/or methallyl alcohol and vinyl esters as demulsifiers for water-containing crude oil |
| CA2168392A1 (en) * | 1996-01-30 | 1997-07-31 | Paul R. Hart | Settling aids for solids in hydrocarbons |
| CN113046115A (en) * | 2021-03-02 | 2021-06-29 | 金浦新材料股份有限公司 | Catalytic cracking slurry oil settling agent and application thereof |
| CN114181731A (en) * | 2021-12-07 | 2022-03-15 | 中海油天津化工研究设计院有限公司 | Micelle dispersion type oil slurry settling agent and preparation method thereof |
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| 陈妹, 杨小龙, 万?懦?: "丙烯酸改性破乳剂合成和性能", 油田化学, no. 03 * |
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