CN113214053A - Refining method of fatty alcohol polyoxyalkylene ether - Google Patents
Refining method of fatty alcohol polyoxyalkylene ether Download PDFInfo
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- CN113214053A CN113214053A CN202110548829.5A CN202110548829A CN113214053A CN 113214053 A CN113214053 A CN 113214053A CN 202110548829 A CN202110548829 A CN 202110548829A CN 113214053 A CN113214053 A CN 113214053A
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- Prior art keywords
- ether
- hours
- fatty alcohol
- adsorbent
- lauryl polyoxyethylene
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 318
- 150000002191 fatty alcohols Chemical class 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000007670 refining Methods 0.000 title claims abstract description 15
- 239000003463 adsorbent Substances 0.000 claims abstract description 71
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002808 molecular sieve Substances 0.000 claims abstract description 25
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000007790 solid phase Substances 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 27
- 238000001179 sorption measurement Methods 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims description 16
- 239000011733 molybdenum Substances 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 238000000746 purification Methods 0.000 claims description 16
- 229910052725 zinc Inorganic materials 0.000 claims description 16
- 239000011701 zinc Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- -1 polyoxyethylene Polymers 0.000 description 131
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 128
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 115
- 238000006243 chemical reaction Methods 0.000 description 107
- 239000000047 product Substances 0.000 description 55
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 50
- 239000012855 volatile organic compound Substances 0.000 description 47
- 238000001816 cooling Methods 0.000 description 39
- 239000000243 solution Substances 0.000 description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 32
- 239000012043 crude product Substances 0.000 description 26
- 239000000203 mixture Substances 0.000 description 26
- 238000003756 stirring Methods 0.000 description 25
- 230000018044 dehydration Effects 0.000 description 20
- 238000006297 dehydration reaction Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000001914 filtration Methods 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 238000005259 measurement Methods 0.000 description 13
- 230000003472 neutralizing effect Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 229920000056 polyoxyethylene ether Polymers 0.000 description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 238000004313 potentiometry Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/36—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
Abstract
The invention relates to a method for refining fatty alcohol polyoxyalkylene ether, which mainly solves the problem of high VOC residual quantity in fatty alcohol polyoxyalkylene ether products in the prior art, and adopts the method for refining the fatty alcohol polyoxyalkylene ether, which comprises the following steps: (1) adsorbing the high-VOC fatty alcohol polyoxyalkylene ether by using an adsorbent; (2) solid-liquid separation is carried out to remove solid phase to obtain the low VOC fatty alcohol polyoxyalkylene ether; the technical scheme that the adsorbent is a ZSM-5 molecular sieve or a ZSM-5 molecular sieve loaded with metal elements better solves the technical problem and can be used for refining production of fatty alcohol polyoxyalkylene ether.
Description
Technical Field
The invention relates to a refining method of fatty alcohol polyoxyalkylene ether, in particular to a method for reducing volatile organic compounds in fatty alcohol polyoxyalkylene ether.
Background
Fatty alcohol polyoxyethylene ether (AEO), also known as polyoxyethylene fatty alcohol ether, has good functions of decontamination, emulsification and wetting, lower irritation and biodegradation, and is the variety which develops the fastest and has the largest dosage in nonionic surfactants. Surfactants of this type are ethers formed by the condensation of polyethylene glycol (PEG) with fatty alcohols, represented by the general formula: RO (CH 2O) nH in which n is the degree of polymerization, varies depending on the degree of polymerization of polyethylene glycol and the kind of fatty alcohol. The ethoxyl number in the fatty alcohol polyoxyethylene ether molecule can be manually adjusted in the synthesis process, so a series of nonionic surfactants with different performances and purposes can be prepared. Fatty alcohol-polyoxyethylene ethers are the most important class of nonionic surfactants. Is widely applied to daily chemical, washing, textile printing and dyeing industries. However, the product obtained by the existing synthesis method of fatty alcohol-polyoxyethylene ether has a relatively high content of volatile organic compounds (VOC for short), so that fatty alcohol-polyoxyethylene ether often has an unpleasant odor, and is now more and more environmentally-friendly, and products with a relatively low V0C content are more and more needed for high-end application.
Disclosure of Invention
The invention aims to provide a refining method of fatty alcohol polyoxyalkylene ether, which has the advantage of low VOC content in the obtained fatty alcohol polyoxyalkylene ether product.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for refining fatty alcohol polyoxyalkylene ether, comprising:
(1) adsorbing the high-VOC fatty alcohol polyoxyalkylene ether by using an adsorbent;
(2) solid-liquid separation is carried out to remove solid phase to obtain the low VOC fatty alcohol polyoxyalkylene ether;
wherein the adsorbent is a ZSM-5 molecular sieve or a ZSM-5 molecular sieve loaded with metal elements.
Due to the use of the adsorbent, the VOC residual quantity in the fatty alcohol polyoxyalkylene ether is obviously reduced.
In the above technical solutions, the specific method for solid-liquid separation is not particularly limited, and those commonly used in the art can be used, and all of them can achieve comparable technical effects. For example, but not limited to, the solid-liquid separation method may be centrifugation, may be filtration, and the like.
In the above technical solution, preferably, the metal element includes at least one selected from the group consisting of iron, nickel, zinc, and molybdenum.
Compared with a pure ZSM-5 molecular sieve, the ZSM-5 molecular sieve loaded with the metal elements has more obvious effect of reducing the residual quantity of VOC in the fatty alcohol polyoxyalkylene ether.
In the above technical solution, it is further preferable that the metal elements include at least two selected from the group consisting of iron, nickel, zinc, and molybdenum, and the two metal elements have an interaction promoting effect in reducing the residual amount of VOC in the fatty alcohol polyoxyalkylene ether. More preferably, the metal elements include at least two selected from the group consisting of nickel, zinc and molybdenum.
In the above technical solution, when the metal element includes at least two selected from the group consisting of iron, nickel, zinc, and molybdenum, the mass ratio between the first metal element and the second metal element is preferably 0.1 to 10, for example, but not limited to, the mass ratio between the first metal element and the second metal element is 0.2, 0.3, 0.4, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, and the like.
By way of non-limiting example, the combination of the first metal element and the second metal element may be:
the first metal element is zinc, and the second metal element is molybdenum; or,
the first metal element is nickel, and the second metal element is zinc; or,
the first metal element is nickel, and the second metal element is molybdenum; or,
the first metal element is iron, and the second metal element is zinc; or,
the first metal element is iron, and the second metal element is molybdenum; or,
the first metal element is iron and the second metal element is nickel.
In the above technical solution, preferably, the metal elements include three metal elements selected from an element group consisting of iron, nickel, zinc, and molybdenum, and at this time, the three metal elements have a combined beneficial effect in reducing VOC residues in the fatty alcohol-polyoxyethylene ether product. Most preferably, the metal elements include all three metal elements selected from the group consisting of nickel, zinc and molybdenum.
In the above technical solution, the ratio of the 1 st metal element to the 2 nd metal element in the three metal elements is preferably: the 3 rd metal element is 1 x y, x and y are independently 0.1-10, such as but not limited to x and y independently 0.2, 0.3, 0.4, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5.
By way of non-limiting example, the 1 st metal element is zinc, the 2 nd metal element is nickel, and the 3 rd metal element is molybdenum.
In the above technical solution, the weight ratio of the metal element to the molecular sieve in the adsorbent is preferably greater than 0 and less than or equal to 0.05. For example, but not limited to, a metal element to molecular sieve weight ratio in the adsorbent of 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, 0.045, and the like.
In the above technical means, the adsorption temperature in the step (1) is not particularly limited, but the adsorption temperature in the step (1) is preferably 50 to 120 ℃. For example, but not limited to, the adsorption temperature in step (1) is 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 110 ℃ and the like. From the comprehensive consideration of the adsorption equilibrium amount and the adsorption speed, the temperature is more preferably 60 to 90 ℃.
In the above technical solution, the adsorption time in the step (1) is preferably more than 0.5 hour. For example, but not limited to, the adsorption time of step (1) is 1.0 hour, 1.5 hours, 2.0 hours, 2.5 hours, 3.0 hours, 3.5 hours, 4.0 hours, 4.5 hours, 5.0 hours, 5.5 hours, and the like. The longer the adsorption time, the more the adsorption process is favorable to reaching equilibrium, but the contribution of the adsorption time to reaching the adsorption equilibrium is gradually reduced along with the extension of time, so that the adsorption time can be controlled to be 1-6 hours, more suitably 1-2 hours.
In the technical scheme, the mass ratio of the high VOC fatty alcohol polyoxyalkylene ether in the step (1) to the adsorbent is preferably 20-200. For example, but not limited to, the mass ratio of the high VOC fatty alcohol polyoxyalkylene ether to the adsorbent in step (1) is 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, etc.
In the above technical scheme, preferably, the high VOC fatty alcohol polyoxyalkylene ether in step (1) is obtained from a synthetic route in which fatty alcohol initiates alkylene oxide polymerization under the catalysis of an alkaline catalyst.
In the above technical solution, it is preferable that the alkylene oxide includes at least one selected from the group consisting of ethylene oxide, propylene oxide and 1, 2-butylene oxide. However, the alkylene oxides are most frequently selected from ethylene oxide and/or propylene oxide, and when the alkylene oxides are selected from ethylene oxide and propylene oxide, the alkylene oxide structural units in the fatty alcohol polyoxyalkylene ether may be randomly or variously blocked.
The specific process conditions obtained as high VOC fatty alcohol polyoxyalkylene ether from the synthetic route to fatty alcohol initiated alkylene oxide polymerization catalyzed by basic catalysts are not particularly limited, but non-limiting illustrative descriptions can be given:
in the above synthetic route, for example, the basic catalyst can be selected from sodium hydroxide, potassium methoxide, sodium methoxide, potassium ethoxide, sodium ethoxide, etc. The amount of catalyst is preferably 0.05% to 0.8% of the weight of the theoretical product.
In the above synthetic route, for example, the fatty alcohol may be a C8-C18 fatty alcohol. For example, but not limited to, the fatty alcohol is at least one selected from the group consisting of C8 fatty alcohol, C9 fatty alcohol, C10 fatty alcohol, C11 fatty alcohol, C12 fatty alcohol, C13 fatty alcohol, C14 fatty alcohol, C15 fatty alcohol, C16 fatty alcohol, C17 fatty alcohol, and C18 fatty alcohol.
In the above synthetic route, for example, the addition number of alkylene oxide in the fatty alcohol polyoxyalkylene ether is 1 to 80, and more preferably 7 to 25. Such as, but not limited to, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, and the like.
In the above synthetic route, for example, the reaction temperature may be selected to be 120 to 180 ℃. For example, but not limited to, 115 deg.C, 120 deg.C, 125 deg.C, 130 deg.C, 135 deg.C, 140 deg.C, 145 deg.C, 160 deg.C, 165 deg.C, 170 deg.C, 175 deg.C, etc.
In the above synthetic route, for example, the reaction pressure may be selected from 0.05 to 0.5MPa, and more specific non-limiting examples thereof are 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa and the like.
In the synthetic route, after the main reaction and the curing are finished, the pH value is usually neutralized to 6-8 by acid after vacuum devolatilization. The acid used for neutralization may be an inorganic acid or an organic acid. The inorganic acid can be selected from sulfuric acid, hydrochloric acid and phosphoric acid, and the phosphoric acid is preferably used in terms of on-site operation sanitation and safety because the phosphoric acid has no oxidation and volatility. Such as but not limited to oxalic acid, adipic acid, tartaric acid.
The fatty alcohol oxyalkylene ether synthesized by the above synthetic route has high VOC content and can be directly adsorbed by an adsorbent, but in order to improve the using effect of the adsorbent, other methods are preferably adopted for pretreatment to reduce the VOC content as much as possible, such as water heating and vacuum dehydration pretreatment. The water heating and vacuum dehydration pretreatment also contributes to the growth of particles of salt generated by neutralization, and is convenient for the removal of salt in the step (2). The amount of water is, for example, but not limited to, 0.1 to 15% of the aliphatic alcohol oxyalkylene ether. The temperature of the vacuum dehydration and the time of the pressure dehydration in the vacuum dehydration are not particularly limited as long as water can be removed. For example, but not limited to, the temperature of vacuum dehydration is 60-120 ℃, the pressure of vacuum dehydration is-0.02-0.095 MPa, and the time of vacuum dehydration can be 0.5-4 hours.
In the above technical solution, preferably, the adsorbent is obtained by a preparation method comprising the following steps:
(a) mixing the hydrogen type ZSM-5 molecular sieve with a solution of metal nitrate;
(b) drying;
(c) and (4) roasting.
In the above technical scheme, the drying temperature in the step (b) is preferably 60-130 ℃. For example, but not limited to, the drying temperature in step (b) is 70 deg.C, 80 deg.C, 90 deg.C, 100 deg.C, 110 deg.C, etc.
In the above technical scheme, the drying time in the step (b) is preferably 3 to 18 hours. For example, but not limited to, the drying time in step (b) is 3.5 hours, 4.0 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 12 hours, 14 hours, 16 hours, and the like.
In the technical scheme, the roasting temperature in the step (c) is preferably 400-700 ℃. For example, but not limited to, the temperature for the calcination in step (c) is 450 deg.C, 500 deg.C, 550 deg.C, 600 deg.C, 650 deg.C.
In the above technical scheme, the roasting temperature in the step (c) is preferably 1-12 hours. For example, but not limited to, the temperature for the calcination in step (c) is selected from 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours, and the like.
In the above technical solutions, the particle size of the adsorbent is not particularly limited, and those skilled in the art can select the particle size as needed. For example, the mesh number of the adsorbent should be 100 mesh or more in view of adsorption speed, and the larger the mesh number of the particles, the better. However, if the particle size is too large, the subsequent filtration is difficult, so that a filter aid is often required.
Unless otherwise specified, the pressure referred to in the present invention is a gauge pressure.
The key of the invention is the selection of the adsorbent, and the technicians in the field can determine other process parameters according to actual needs and can obtain comparable technical effects.
The method for measuring the residual quantity of the volatile organic compounds in the embodiment of the invention is carried out according to GB/T35862-2018 (a method for measuring the residual quantity of the volatile organic compounds of the surfactant by using a headspace gas chromatography-mass spectrometry (GC-MS) combination).
The pH test method in the embodiment of the invention is carried out according to GB/T6368-2008 (potentiometry for measuring pH value of surfactant aqueous solution).
The inventor finds through experiments that the content of the volatile organic compound of the fatty alcohol-polyoxyethylene ether can be greatly reduced after the method is used.
The present invention will be further described with reference to the following examples.
Detailed Description
[ example 1 ]
1. Synthesis of lauryl polyoxyethylene (9) ether
1 mol of dodecanol and 1 g of KOH were added to a 1.5L stirred autoclave, which was sealed and stirred. The air in the reaction vessel was replaced with nitrogen three times, and then vacuum was applied at 100 ℃ and-0.09 MPa for 30 min. Then ethylene oxide was introduced into the reaction vessel, the reaction temperature was controlled at 140 ℃ and the reaction pressure was controlled at 0.2MPa until 9 moles of ethylene oxide was introduced, and then the mixture was stopped to complete the main reaction. Maintaining the temperature of the reaction kettle at 140 ℃ for curing until the pressure of the reaction kettle does not decrease any more, indicating that the curing reaction is finished, vacuumizing for 30min at the pressure of-0.09 MPa and the temperature of 110 ℃, cooling to 80 ℃, neutralizing with phosphoric acid until the pH value is 6.5, and cooling to room temperature to obtain a crude product of lauryl polyoxyethylene (9) ether.
2. Preparation of the adsorbent
100 g of a 180-mesh hydrogen type ZSM-5 molecular sieve and 50 g of a metal nitrate aqueous solution (containing 1 g of zinc, 1 g of nickel and 1 g of molybdenum) are mixed, dried at 90 ℃ for 8 hours, roasted at 500 ℃ for 5 hours, crushed and sieved by a 100-mesh sieve to obtain the adsorbent.
3. Purification of lauryl polyoxyethylene (9) ether
3.1 pretreatment of lauryl polyoxyethylene (9) ether
Mixing deionized water and the crude product of the lauryl polyoxyethylene (9) ether in the step 1 according to a weight ratio of 5:100, stirring at a constant temperature of 70 ℃ for 1 hour, carrying out vacuum dehydration at a temperature of 110 ℃ and a pressure of-0.090 MPa for 3 hours, and cooling to 80 ℃ to obtain a lauryl polyoxyethylene (9) ether pretreatment product.
3.2 adsorption treatment of lauryl polyoxyethylene (9) ether
Mixing 100 grams of the dodecanol polyoxyethylene (9) ether pretreatment product of step 3.1 with 1 gram of the adsorbent of step 2; stirring was carried out at a constant temperature of 80 ℃ for 2 hours. Filtering the solution while the solution is hot until the filtrate is clear to obtain a refined product of the lauryl polyoxyethylene (9) ether.
The residual amount of volatile organic compounds in the refined product of lauryl polyoxyethylene (9) ether was measured.
For comparison, the composition of the adsorbent and the measurement results of the residual amount of volatile organic compounds are shown in Table 1.
[ example 2 ]
1. Synthesis of lauryl polyoxyethylene (9) ether
1 mol of dodecanol and 1 g of KOH were added to a 1.5L stirred autoclave, which was sealed and stirred. The air in the reaction vessel was replaced with nitrogen three times, and then vacuum was applied at 100 ℃ and-0.09 MPa for 30 min. Then ethylene oxide was introduced into the reaction vessel, the reaction temperature was controlled at 140 ℃ and the reaction pressure was controlled at 0.2MPa until 9 moles of ethylene oxide was introduced, and then the mixture was stopped to complete the main reaction. Maintaining the temperature of the reaction kettle at 140 ℃ for curing until the pressure of the reaction kettle does not decrease any more, indicating that the curing reaction is finished, vacuumizing for 30min at the pressure of-0.09 MPa and the temperature of 110 ℃, cooling to 80 ℃, neutralizing with phosphoric acid until the pH value is 6.5, and cooling to room temperature to obtain a crude product of lauryl polyoxyethylene (9) ether.
2. Preparation of the adsorbent
100 g of 180-mesh hydrogen type ZSM-5 molecular sieve and 50 g of metal nitrate aqueous solution (containing 2 g of zinc and 2 g of molybdenum) are mixed, dried at 90 ℃ for 8 hours, roasted at 500 ℃ for 5 hours, crushed and sieved by a 100-mesh sieve to obtain the adsorbent.
3. Purification of lauryl polyoxyethylene (9) ether
3.1 pretreatment of lauryl polyoxyethylene (9) ether
Mixing deionized water and the crude product of the lauryl polyoxyethylene (9) ether in the step 1 according to a weight ratio of 5:100, stirring at a constant temperature of 70 ℃ for 1 hour, carrying out vacuum dehydration at a temperature of 110 ℃ and a pressure of-0.090 MPa for 3 hours, and cooling to 80 ℃ to obtain a lauryl polyoxyethylene (9) ether pretreatment product.
3.2 adsorption treatment of lauryl polyoxyethylene (9) ether
Mixing 100 grams of the dodecanol polyoxyethylene (9) ether pretreatment product of step 3.1 with 1 gram of the adsorbent of step 2; stirring was carried out at a constant temperature of 80 ℃ for 2 hours. Filtering the solution while the solution is hot until the filtrate is clear to obtain a refined product of the lauryl polyoxyethylene (9) ether.
The residual amount of volatile organic compounds in the refined product of lauryl polyoxyethylene (9) ether was measured.
For comparison, the composition of the adsorbent and the measurement results of the residual amount of volatile organic compounds are shown in Table 1.
[ example 3 ]
1. Synthesis of lauryl polyoxyethylene (9) ether
1 mol of dodecanol and 1 g of KOH were added to a 1.5L stirred autoclave, which was sealed and stirred. The air in the reaction vessel was replaced with nitrogen three times, and then vacuum was applied at 100 ℃ and-0.09 MPa for 30 min. Then ethylene oxide was introduced into the reaction vessel, the reaction temperature was controlled at 140 ℃ and the reaction pressure was controlled at 0.2MPa until 9 moles of ethylene oxide was introduced, and then the mixture was stopped to complete the main reaction. Maintaining the temperature of the reaction kettle at 140 ℃ for curing until the pressure of the reaction kettle does not decrease any more, indicating that the curing reaction is finished, vacuumizing for 30min at the pressure of-0.09 MPa and the temperature of 110 ℃, cooling to 80 ℃, neutralizing with phosphoric acid until the pH value is 6.5, and cooling to room temperature to obtain a crude product of lauryl polyoxyethylene (9) ether.
2. Preparation of the adsorbent
100 g of a 180-mesh hydrogen type ZSM-5 molecular sieve and 50 g of a metal nitrate aqueous solution (wherein 3 g of nickel and 1 g of zinc are contained) are mixed, dried at 90 ℃ for 8 hours, roasted at 500 ℃ for 5 hours, crushed and sieved by a 100-mesh sieve to obtain the adsorbent.
3. Purification of lauryl polyoxyethylene (9) ether
3.1 pretreatment of lauryl polyoxyethylene (9) ether
Mixing deionized water and the crude product of the lauryl polyoxyethylene (9) ether in the step 1 according to a weight ratio of 5:100, stirring at a constant temperature of 70 ℃ for 1 hour, carrying out vacuum dehydration at a temperature of 110 ℃ and a pressure of-0.090 MPa for 3 hours, and cooling to 80 ℃ to obtain a lauryl polyoxyethylene (9) ether pretreatment product.
3.2 adsorption treatment of lauryl polyoxyethylene (9) ether
Mixing 100 grams of the dodecanol polyoxyethylene (9) ether pretreatment product of step 3.1 with 1 gram of the adsorbent of step 2; stirring was carried out at a constant temperature of 80 ℃ for 2 hours. Filtering the solution while the solution is hot until the filtrate is clear to obtain a refined product of the lauryl polyoxyethylene (9) ether.
The residual amount of volatile organic compounds in the refined product of lauryl polyoxyethylene (9) ether was measured.
For comparison, the composition of the adsorbent and the measurement results of the residual amount of volatile organic compounds are shown in Table 1.
[ example 4 ]
1. Synthesis of lauryl polyoxyethylene (9) ether
1 mol of dodecanol and 1 g of KOH were added to a 1.5L stirred autoclave, which was sealed and stirred. The air in the reaction vessel was replaced with nitrogen three times, and then vacuum was applied at 100 ℃ and-0.09 MPa for 30 min. Then ethylene oxide was introduced into the reaction vessel, the reaction temperature was controlled at 140 ℃ and the reaction pressure was controlled at 0.2MPa until 9 moles of ethylene oxide was introduced, and then the mixture was stopped to complete the main reaction. Maintaining the temperature of the reaction kettle at 140 ℃ for curing until the pressure of the reaction kettle does not decrease any more, indicating that the curing reaction is finished, vacuumizing for 30min at the pressure of-0.09 MPa and the temperature of 110 ℃, cooling to 80 ℃, neutralizing with phosphoric acid until the pH value is 6.5, and cooling to room temperature to obtain a crude product of lauryl polyoxyethylene (9) ether.
2. Preparation of the adsorbent
100 g of a 180-mesh hydrogen type ZSM-5 molecular sieve and 50 g of metal nitrate aqueous solution (containing 3 g of nickel and 1 g of molybdenum) are mixed, dried at 90 ℃ for 8 hours, roasted at 500 ℃ for 5 hours, crushed and sieved by a 100-mesh sieve to obtain the adsorbent.
3. Purification of lauryl polyoxyethylene (9) ether
3.1 pretreatment of lauryl polyoxyethylene (9) ether
Mixing deionized water and the crude product of the lauryl polyoxyethylene (9) ether in the step 1 according to a weight ratio of 5:100, stirring at a constant temperature of 70 ℃ for 1 hour, carrying out vacuum dehydration at a temperature of 110 ℃ and a pressure of-0.090 MPa for 3 hours, and cooling to 80 ℃ to obtain a lauryl polyoxyethylene (9) ether pretreatment product.
3.2 adsorption treatment of lauryl polyoxyethylene (9) ether
Mixing 100 grams of the dodecanol polyoxyethylene (9) ether pretreatment product of step 3.1 with 1 gram of the adsorbent of step 2; stirring was carried out at a constant temperature of 80 ℃ for 2 hours. Filtering the solution while the solution is hot until the filtrate is clear to obtain a refined product of the lauryl polyoxyethylene (9) ether.
The residual amount of volatile organic compounds in the refined product of lauryl polyoxyethylene (9) ether was measured.
For comparison, the composition of the adsorbent and the measurement results of the residual amount of volatile organic compounds are shown in Table 1.
[ example 5 ]
1. Synthesis of lauryl polyoxyethylene (9) ether
1 mol of dodecanol and 1 g of KOH were added to a 1.5L stirred autoclave, which was sealed and stirred. The air in the reaction vessel was replaced with nitrogen three times, and then vacuum was applied at 100 ℃ and-0.09 MPa for 30 min. Then ethylene oxide was introduced into the reaction vessel, the reaction temperature was controlled at 140 ℃ and the reaction pressure was controlled at 0.2MPa until 9 moles of ethylene oxide was introduced, and then the mixture was stopped to complete the main reaction. Maintaining the temperature of the reaction kettle at 140 ℃ for curing until the pressure of the reaction kettle does not decrease any more, indicating that the curing reaction is finished, vacuumizing for 30min at the pressure of-0.09 MPa and the temperature of 110 ℃, cooling to 80 ℃, neutralizing with phosphoric acid until the pH value is 6.5, and cooling to room temperature to obtain a crude product of lauryl polyoxyethylene (9) ether.
2. Preparation of the adsorbent
100 g of a 180-mesh hydrogen type ZSM-5 molecular sieve and 50 g of a metal nitrate aqueous solution (containing 1 g of iron and 3 g of zinc) are mixed, dried at 90 ℃ for 8 hours, roasted at 500 ℃ for 5 hours, crushed and sieved by a 100-mesh sieve to obtain the adsorbent.
3. Purification of lauryl polyoxyethylene (9) ether
3.1 pretreatment of lauryl polyoxyethylene (9) ether
Mixing deionized water and the crude product of the lauryl polyoxyethylene (9) ether in the step 1 according to a weight ratio of 5:100, stirring at a constant temperature of 70 ℃ for 1 hour, carrying out vacuum dehydration at a temperature of 110 ℃ and a pressure of-0.090 MPa for 3 hours, and cooling to 80 ℃ to obtain a lauryl polyoxyethylene (9) ether pretreatment product.
3.2 adsorption treatment of lauryl polyoxyethylene (9) ether
Mixing 100 grams of the dodecanol polyoxyethylene (9) ether pretreatment product of step 3.1 with 1 gram of the adsorbent of step 2; stirring was carried out at a constant temperature of 80 ℃ for 2 hours. Filtering the solution while the solution is hot until the filtrate is clear to obtain a refined product of the lauryl polyoxyethylene (9) ether.
The residual amount of volatile organic compounds in the refined product of lauryl polyoxyethylene (9) ether was measured.
For comparison, the composition of the adsorbent and the measurement results of the residual amount of volatile organic compounds are shown in Table 1.
[ example 6 ]
1. Synthesis of lauryl polyoxyethylene (9) ether
1 mol of dodecanol and 1 g of KOH were added to a 1.5L stirred autoclave, which was sealed and stirred. The air in the reaction vessel was replaced with nitrogen three times, and then vacuum was applied at 100 ℃ and-0.09 MPa for 30 min. Then ethylene oxide was introduced into the reaction vessel, the reaction temperature was controlled at 140 ℃ and the reaction pressure was controlled at 0.2MPa until 9 moles of ethylene oxide was introduced, and then the mixture was stopped to complete the main reaction. Maintaining the temperature of the reaction kettle at 140 ℃ for curing until the pressure of the reaction kettle does not decrease any more, indicating that the curing reaction is finished, vacuumizing for 30min at the pressure of-0.09 MPa and the temperature of 110 ℃, cooling to 80 ℃, neutralizing with phosphoric acid until the pH value is 6.5, and cooling to room temperature to obtain a crude product of lauryl polyoxyethylene (9) ether.
2. Preparation of the adsorbent
100 g of a 180-mesh hydrogen type ZSM-5 molecular sieve and 50 g of metal nitrate aqueous solution (containing 1 g of iron and 3 g of molybdenum) are mixed, dried at 90 ℃ for 8 hours, roasted at 500 ℃ for 5 hours, crushed and sieved by a 100-mesh sieve to obtain the adsorbent.
3. Purification of lauryl polyoxyethylene (9) ether
3.1 pretreatment of lauryl polyoxyethylene (9) ether
Mixing deionized water and the crude product of the lauryl polyoxyethylene (9) ether in the step 1 according to a weight ratio of 5:100, stirring at a constant temperature of 70 ℃ for 1 hour, carrying out vacuum dehydration at a temperature of 110 ℃ and a pressure of-0.090 MPa for 3 hours, and cooling to 80 ℃ to obtain a lauryl polyoxyethylene (9) ether pretreatment product.
3.2 adsorption treatment of lauryl polyoxyethylene (9) ether
Mixing 100 grams of the dodecanol polyoxyethylene (9) ether pretreatment product of step 3.1 with 1 gram of the adsorbent of step 2; stirring was carried out at a constant temperature of 80 ℃ for 2 hours. Filtering the solution while the solution is hot until the filtrate is clear to obtain a refined product of the lauryl polyoxyethylene (9) ether.
The residual amount of volatile organic compounds in the refined product of lauryl polyoxyethylene (9) ether was measured.
For comparison, the composition of the adsorbent and the measurement results of the residual amount of volatile organic compounds are shown in Table 1.
[ example 7 ]
1. Synthesis of lauryl polyoxyethylene (9) ether
1 mol of dodecanol and 1 g of KOH were added to a 1.5L stirred autoclave, which was sealed and stirred. The air in the reaction vessel was replaced with nitrogen three times, and then vacuum was applied at 100 ℃ and-0.09 MPa for 30 min. Then ethylene oxide was introduced into the reaction vessel, the reaction temperature was controlled at 140 ℃ and the reaction pressure was controlled at 0.2MPa until 9 moles of ethylene oxide was introduced, and then the mixture was stopped to complete the main reaction. Maintaining the temperature of the reaction kettle at 140 ℃ for curing until the pressure of the reaction kettle does not decrease any more, indicating that the curing reaction is finished, vacuumizing for 30min at the pressure of-0.09 MPa and the temperature of 110 ℃, cooling to 80 ℃, neutralizing with phosphoric acid until the pH value is 6.5, and cooling to room temperature to obtain a crude product of lauryl polyoxyethylene (9) ether.
2. Preparation of the adsorbent
100 g of a 180-mesh hydrogen type ZSM-5 molecular sieve and 50 g of a metal nitrate aqueous solution (containing 1 g of iron and 3 g of nickel) are mixed, dried at 90 ℃ for 8 hours, roasted at 500 ℃ for 5 hours, crushed and sieved by a 100-mesh sieve to obtain the adsorbent.
3. Purification of lauryl polyoxyethylene (9) ether
3.1 pretreatment of lauryl polyoxyethylene (9) ether
Mixing deionized water and the crude product of the lauryl polyoxyethylene (9) ether in the step 1 according to a weight ratio of 5:100, stirring at a constant temperature of 70 ℃ for 1 hour, carrying out vacuum dehydration at a temperature of 110 ℃ and a pressure of-0.090 MPa for 3 hours, and cooling to 80 ℃ to obtain a lauryl polyoxyethylene (9) ether pretreatment product.
3.2 adsorption treatment of lauryl polyoxyethylene (9) ether
Mixing 100 grams of the dodecanol polyoxyethylene (9) ether pretreatment product of step 3.1 with 1 gram of the adsorbent of step 2; stirring was carried out at a constant temperature of 80 ℃ for 2 hours. Filtering the solution while the solution is hot until the filtrate is clear to obtain a refined product of the lauryl polyoxyethylene (9) ether.
The residual amount of volatile organic compounds in the refined product of lauryl polyoxyethylene (9) ether was measured.
For comparison, the composition of the adsorbent and the measurement results of the residual amount of volatile organic compounds are shown in Table 1.
[ example 8 ]
1. Synthesis of lauryl polyoxyethylene (9) ether
1 mol of dodecanol and 1 g of KOH were added to a 1.5L stirred autoclave, which was sealed and stirred. The air in the reaction vessel was replaced with nitrogen three times, and then vacuum was applied at 100 ℃ and-0.09 MPa for 30 min. Then ethylene oxide was introduced into the reaction vessel, the reaction temperature was controlled at 140 ℃ and the reaction pressure was controlled at 0.2MPa until 9 moles of ethylene oxide was introduced, and then the mixture was stopped to complete the main reaction. Maintaining the temperature of the reaction kettle at 140 ℃ for curing until the pressure of the reaction kettle does not decrease any more, indicating that the curing reaction is finished, vacuumizing for 30min at the pressure of-0.09 MPa and the temperature of 110 ℃, cooling to 80 ℃, neutralizing with phosphoric acid until the pH value is 6.5, and cooling to room temperature to obtain a crude product of lauryl polyoxyethylene (9) ether.
2. Preparation of the adsorbent
100 g of a 180-mesh hydrogen type ZSM-5 molecular sieve and 50 g of a metal nitrate aqueous solution (containing 4 g of iron) are mixed, dried for 8 hours at 90 ℃, roasted for 5 hours at 500 ℃, crushed and sieved by a 100-mesh sieve to obtain the adsorbent.
3. Purification of lauryl polyoxyethylene (9) ether
3.1 pretreatment of lauryl polyoxyethylene (9) ether
Mixing deionized water and the crude product of the lauryl polyoxyethylene (9) ether in the step 1 according to a weight ratio of 5:100, stirring at a constant temperature of 70 ℃ for 1 hour, carrying out vacuum dehydration at a temperature of 110 ℃ and a pressure of-0.090 MPa for 3 hours, and cooling to 80 ℃ to obtain a lauryl polyoxyethylene (9) ether pretreatment product.
3.2 adsorption treatment of lauryl polyoxyethylene (9) ether
Mixing 100 grams of the dodecanol polyoxyethylene (9) ether pretreatment product of step 3.1 with 1 gram of the adsorbent of step 2; stirring was carried out at a constant temperature of 80 ℃ for 2 hours. Filtering the solution while the solution is hot until the filtrate is clear to obtain a refined product of the lauryl polyoxyethylene (9) ether.
The residual amount of volatile organic compounds in the refined product of lauryl polyoxyethylene (9) ether was measured.
For comparison, the composition of the adsorbent and the measurement results of the residual amount of volatile organic compounds are shown in Table 1.
[ example 9 ]
1. Synthesis of lauryl polyoxyethylene (9) ether
1 mol of dodecanol and 1 g of KOH were added to a 1.5L stirred autoclave, which was sealed and stirred. The air in the reaction vessel was replaced with nitrogen three times, and then vacuum was applied at 100 ℃ and-0.09 MPa for 30 min. Then ethylene oxide was introduced into the reaction vessel, the reaction temperature was controlled at 140 ℃ and the reaction pressure was controlled at 0.2MPa until 9 moles of ethylene oxide was introduced, and then the mixture was stopped to complete the main reaction. Maintaining the temperature of the reaction kettle at 140 ℃ for curing until the pressure of the reaction kettle does not decrease any more, indicating that the curing reaction is finished, vacuumizing for 30min at the pressure of-0.09 MPa and the temperature of 110 ℃, cooling to 80 ℃, neutralizing with phosphoric acid until the pH value is 6.5, and cooling to room temperature to obtain a crude product of lauryl polyoxyethylene (9) ether.
2. Preparation of the adsorbent
100 g of a 180-mesh hydrogen type ZSM-5 molecular sieve and 50 g of a metal nitrate aqueous solution (containing 4 g of nickel) are mixed, dried for 8 hours at 90 ℃, roasted for 5 hours at 500 ℃, crushed and sieved by a 100-mesh sieve to obtain the adsorbent.
3. Purification of lauryl polyoxyethylene (9) ether
3.1 pretreatment of lauryl polyoxyethylene (9) ether
Mixing deionized water and the crude product of the lauryl polyoxyethylene (9) ether in the step 1 according to a weight ratio of 5:100, stirring at a constant temperature of 70 ℃ for 1 hour, carrying out vacuum dehydration at a temperature of 110 ℃ and a pressure of-0.090 MPa for 3 hours, and cooling to 80 ℃ to obtain a lauryl polyoxyethylene (9) ether pretreatment product.
3.2 adsorption treatment of lauryl polyoxyethylene (9) ether
Mixing 100 grams of the dodecanol polyoxyethylene (9) ether pretreatment product of step 3.1 with 1 gram of the adsorbent of step 2; stirring was carried out at a constant temperature of 80 ℃ for 2 hours. Filtering the solution while the solution is hot until the filtrate is clear to obtain a refined product of the lauryl polyoxyethylene (9) ether.
The residual amount of volatile organic compounds in the refined product of lauryl polyoxyethylene (9) ether was measured.
For comparison, the composition of the adsorbent and the measurement results of the residual amount of volatile organic compounds are shown in Table 1.
[ example 10 ]
1. Synthesis of lauryl polyoxyethylene (9) ether
1 mol of dodecanol and 1 g of KOH were added to a 1.5L stirred autoclave, which was sealed and stirred. The air in the reaction vessel was replaced with nitrogen three times, and then vacuum was applied at 100 ℃ and-0.09 MPa for 30 min. Then ethylene oxide was introduced into the reaction vessel, the reaction temperature was controlled at 140 ℃ and the reaction pressure was controlled at 0.2MPa until 9 moles of ethylene oxide was introduced, and then the mixture was stopped to complete the main reaction. Maintaining the temperature of the reaction kettle at 140 ℃ for curing until the pressure of the reaction kettle does not decrease any more, indicating that the curing reaction is finished, vacuumizing for 30min at the pressure of-0.09 MPa and the temperature of 110 ℃, cooling to 80 ℃, neutralizing with phosphoric acid until the pH value is 6.5, and cooling to room temperature to obtain a crude product of lauryl polyoxyethylene (9) ether.
2. Preparation of the adsorbent
100 g of 180-mesh hydrogen type ZSM-5 molecular sieve and 50 g of metal nitrate aqueous solution (containing 4 g of zinc) are mixed, dried for 8 hours at 90 ℃, roasted for 5 hours at 500 ℃, crushed and sieved by a 100-mesh sieve to obtain the adsorbent.
3. Purification of lauryl polyoxyethylene (9) ether
3.1 pretreatment of lauryl polyoxyethylene (9) ether
Mixing deionized water and the crude product of the lauryl polyoxyethylene (9) ether in the step 1 according to a weight ratio of 5:100, stirring at a constant temperature of 70 ℃ for 1 hour, carrying out vacuum dehydration at a temperature of 110 ℃ and a pressure of-0.090 MPa for 3 hours, and cooling to 80 ℃ to obtain a lauryl polyoxyethylene (9) ether pretreatment product.
3.2 adsorption treatment of lauryl polyoxyethylene (9) ether
Mixing 100 grams of the dodecanol polyoxyethylene (9) ether pretreatment product of step 3.1 with 1 gram of the adsorbent of step 2; stirring was carried out at a constant temperature of 80 ℃ for 2 hours. Filtering the solution while the solution is hot until the filtrate is clear to obtain a refined product of the lauryl polyoxyethylene (9) ether.
The residual amount of volatile organic compounds in the refined product of lauryl polyoxyethylene (9) ether was measured.
For comparison, the composition of the adsorbent and the measurement results of the residual amount of volatile organic compounds are shown in Table 1.
[ example 11 ]
1. Synthesis of lauryl polyoxyethylene (9) ether
1 mol of dodecanol and 1 g of KOH were added to a 1.5L stirred autoclave, which was sealed and stirred. The air in the reaction vessel was replaced with nitrogen three times, and then vacuum was applied at 100 ℃ and-0.09 MPa for 30 min. Then ethylene oxide was introduced into the reaction vessel, the reaction temperature was controlled at 140 ℃ and the reaction pressure was controlled at 0.2MPa until 9 moles of ethylene oxide was introduced, and then the mixture was stopped to complete the main reaction. Maintaining the temperature of the reaction kettle at 140 ℃ for curing until the pressure of the reaction kettle does not decrease any more, indicating that the curing reaction is finished, vacuumizing for 30min at the pressure of-0.09 MPa and the temperature of 110 ℃, cooling to 80 ℃, neutralizing with phosphoric acid until the pH value is 6.5, and cooling to room temperature to obtain a crude product of lauryl polyoxyethylene (9) ether.
2. Preparation of the adsorbent
100 g of a 180-mesh hydrogen type ZSM-5 molecular sieve and 50 g of a metal nitrate aqueous solution (containing 4 g of molybdenum) are mixed, dried for 8 hours at 90 ℃, roasted for 5 hours at 500 ℃, crushed and sieved by a 100-mesh sieve to obtain the adsorbent.
3. Purification of lauryl polyoxyethylene (9) ether
3.1 pretreatment of lauryl polyoxyethylene (9) ether
Mixing deionized water and the crude product of the lauryl polyoxyethylene (9) ether in the step 1 according to a weight ratio of 5:100, stirring at a constant temperature of 70 ℃ for 1 hour, carrying out vacuum dehydration at a temperature of 110 ℃ and a pressure of-0.090 MPa for 3 hours, and cooling to 80 ℃ to obtain a lauryl polyoxyethylene (9) ether pretreatment product.
3.2 adsorption treatment of lauryl polyoxyethylene (9) ether
Mixing 100 grams of the dodecanol polyoxyethylene (9) ether pretreatment product of step 3.1 with 1 gram of the adsorbent of step 2; stirring was carried out at a constant temperature of 80 ℃ for 2 hours. Filtering the solution while the solution is hot until the filtrate is clear to obtain a refined product of the lauryl polyoxyethylene (9) ether.
The residual amount of volatile organic compounds in the refined product of lauryl polyoxyethylene (9) ether was measured.
For comparison, the composition of the adsorbent and the measurement results of the residual amount of volatile organic compounds are shown in Table 1.
[ example 12 ]
1. Synthesis of lauryl polyoxyethylene (9) ether
1 mol of dodecanol and 1 g of KOH were added to a 1.5L stirred autoclave, which was sealed and stirred. The air in the reaction vessel was replaced with nitrogen three times, and then vacuum was applied at 100 ℃ and-0.09 MPa for 30 min. Then ethylene oxide was introduced into the reaction vessel, the reaction temperature was controlled at 140 ℃ and the reaction pressure was controlled at 0.2MPa until 9 moles of ethylene oxide was introduced, and then the mixture was stopped to complete the main reaction. Maintaining the temperature of the reaction kettle at 140 ℃ for curing until the pressure of the reaction kettle does not decrease any more, indicating that the curing reaction is finished, vacuumizing for 30min at the pressure of-0.09 MPa and the temperature of 110 ℃, cooling to 80 ℃, neutralizing with phosphoric acid until the pH value is 6.5, and cooling to room temperature to obtain a crude product of lauryl polyoxyethylene (9) ether.
2. Adsorbent and process for producing the same
A hydrogen type ZSM-5 molecular sieve of 180 degrees is used as an adsorbent, and the catalyst is dried for 8 hours at 90 degrees before being used for refining lauryl polyoxyethylene (9) ether and is roasted for 5 hours at 500 degrees.
3. Purification of lauryl polyoxyethylene (9) ether
3.1 pretreatment of lauryl polyoxyethylene (9) ether
Mixing deionized water and the crude product of the lauryl polyoxyethylene (9) ether in the step 1 according to a weight ratio of 5:100, stirring at a constant temperature of 70 ℃ for 1 hour, carrying out vacuum dehydration at a temperature of 110 ℃ and a pressure of-0.090 MPa for 3 hours, and cooling to 80 ℃ to obtain a lauryl polyoxyethylene (9) ether pretreatment product.
3.2 adsorption treatment of lauryl polyoxyethylene (9) ether
Mixing 100 grams of the dodecanol polyoxyethylene (9) ether pretreatment product of step 3.1 with 1 gram of the adsorbent of step 2; stirring was carried out at a constant temperature of 80 ℃ for 2 hours. Filtering the solution while the solution is hot until the filtrate is clear to obtain a refined product of the lauryl polyoxyethylene (9) ether.
The residual amount of volatile organic compounds in the refined product of lauryl polyoxyethylene (9) ether was measured.
For comparison, the composition of the adsorbent and the measurement results of the residual amount of volatile organic compounds are shown in Table 1.
[ COMPARATIVE EXAMPLE ]
1. Synthesis of lauryl polyoxyethylene (9) ether
1 mol of dodecanol and 1 g of KOH were added to a 1.5L stirred autoclave, which was sealed and stirred. The air in the reaction vessel was replaced with nitrogen three times, and then vacuum was applied at 100 ℃ and-0.09 MPa for 30 min. Then ethylene oxide was introduced into the reaction vessel, the reaction temperature was controlled at 140 ℃ and the reaction pressure was controlled at 0.2MPa until 9 moles of ethylene oxide was introduced, and then the mixture was stopped to complete the main reaction. Maintaining the temperature of the reaction kettle at 140 ℃ for curing until the pressure of the reaction kettle does not decrease any more, indicating that the curing reaction is finished, vacuumizing for 30min at the pressure of-0.09 MPa and the temperature of 110 ℃, cooling to 80 ℃, neutralizing with phosphoric acid until the pH value is 6.5, and cooling to room temperature to obtain a crude product of lauryl polyoxyethylene (9) ether.
2. Adsorbent and process for producing the same
No adsorbent is used.
3. Purification of lauryl polyoxyethylene (9) ether
Mixing deionized water and the crude product of the lauryl polyoxyethylene (9) ether in the step 1 according to a weight ratio of 5:100, stirring for 1 hour at a constant temperature of 70 ℃, vacuum dehydrating for 3 hours at a temperature of 110 ℃ and a pressure of-0.090 MPa, and cooling to 80 ℃ to obtain a refined product of the lauryl polyoxyethylene (9) ether.
The residual amount of volatile organic compounds in the refined product of lauryl polyoxyethylene (9) ether was measured.
For comparison, the composition of the adsorbent and the measurement results of the residual amount of volatile organic compounds are shown in Table 1.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
TABLE 1
Note: VOC refers to volatile organic compounds.
Claims (10)
1. A method for refining fatty alcohol polyoxyalkylene ether, comprising:
(1) adsorbing the high-VOC fatty alcohol polyoxyalkylene ether by using an adsorbent;
(2) solid-liquid separation is carried out to remove solid phase to obtain the low VOC fatty alcohol polyoxyalkylene ether;
wherein the adsorbent is a ZSM-5 molecular sieve or a ZSM-5 molecular sieve loaded with metal elements.
2. The refining method according to claim 1, wherein the metal element includes at least one selected from the group consisting of iron, nickel, zinc, and molybdenum.
3. The purification process as claimed in claim 1, wherein the weight ratio of the metal element to the molecular sieve in the adsorbent is 0 or more and 0.05 or less.
4. The purification process according to claim 1, wherein the adsorption temperature in the step (1) is 50 to 120 ℃.
5. The purification process as claimed in claim 1, wherein the adsorption time in the step (1) is more than 0.5 hour. Preferably 1 to 6 hours, more preferably 1 to 2 hours.
6. The refining method as claimed in claim 1, wherein the mass ratio of the high VOC fatty alcohol polyoxyalkylene ether to the adsorbent in step (1) is 20-200.
7. The refining process of claim 1, wherein the high VOC fatty alcohol polyoxyalkylene ether of step (1) is obtained from a synthetic route in which an aliphatic alcohol initiates alkylene oxide polymerization under the catalysis of an alkaline catalyst. Preferably, the alkylene oxide includes at least one selected from the group consisting of ethylene oxide, propylene oxide and 1, 2-butylene oxide.
8. The refining method according to claim 1, wherein the adsorbent is obtained by a production method comprising:
(a) mixing the hydrogen type ZSM-5 molecular sieve with a solution of metal nitrate;
(b) drying;
(c) and (4) roasting.
9. The method according to claim 8, wherein the drying temperature in the step (b) is 60 to 130 ℃. And/or preferably the drying time is 3 to 18 hours.
10. The refining method according to claim 8, wherein the calcination temperature in the step (c) is 400 to 700 ℃. And/or preferably the roasting time is 1-12 hours.
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Denomination of invention: Refining method of fatty alcohol polyoxyalkylene ether Granted publication date: 20220805 Pledgee: Shanghai Rural Commercial Bank Co.,Ltd. Jinshan sub branch Pledgor: SHANGHAI DUOLUN CHEMICAL Co.,Ltd. Registration number: Y2024310000328 |