CN101337877A - Method for preparing higher fatty acid alkali salt - Google Patents
Method for preparing higher fatty acid alkali salt Download PDFInfo
- Publication number
- CN101337877A CN101337877A CNA2008100300829A CN200810030082A CN101337877A CN 101337877 A CN101337877 A CN 101337877A CN A2008100300829 A CNA2008100300829 A CN A2008100300829A CN 200810030082 A CN200810030082 A CN 200810030082A CN 101337877 A CN101337877 A CN 101337877A
- Authority
- CN
- China
- Prior art keywords
- fatty acid
- acid
- higher fatty
- preparation
- alkali salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 37
- 239000000194 fatty acid Substances 0.000 title claims abstract description 37
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 37
- -1 fatty acid alkali salt Chemical class 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 16
- 238000009413 insulation Methods 0.000 claims abstract description 11
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims description 29
- 239000006185 dispersion Substances 0.000 claims description 13
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 239000000080 wetting agent Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000003595 mist Substances 0.000 claims description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 claims description 4
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical class CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 150000007518 monoprotic acids Chemical class 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 claims description 3
- 229940082004 sodium laurate Drugs 0.000 claims description 3
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 claims description 3
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 23
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 10
- 235000021355 Stearic acid Nutrition 0.000 description 9
- 150000002632 lipids Chemical class 0.000 description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 9
- 239000008117 stearic acid Substances 0.000 description 9
- 230000004580 weight loss Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 5
- 239000008116 calcium stearate Substances 0.000 description 5
- 235000013539 calcium stearate Nutrition 0.000 description 5
- 235000019359 magnesium stearate Nutrition 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- DEISLDFBMJLVTC-UHFFFAOYSA-N 8-(difluoromethoxy)-1-ethyl-6-fluoro-7-[4-(2-methoxyphenyl)piperazin-1-yl]-4-oxoquinoline-3-carboxylic acid Chemical compound FC(F)OC1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N(CC1)CCN1C1=CC=CC=C1OC DEISLDFBMJLVTC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000012255 powdered metal Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of higher fatty acid alkaline earth metal salt, which comprises the following steps: pre-mixing and dispersing fused higher fatty acid and micro-powdery alkaline earth metal oxide or hydrate, continuously feeding into a high-speed mixer capable of controlling the pre-mixing time together with a water solution containing a catalyst and a moistening agent, continuously outputting to a heat-insulation tank, keeping for a certain period of time at the proper temperature, and pulverizing to obtain a powdery higher fatty acid alkaline earth metal salt product. The preparation method has the advantages of simple process, simple equipment, mild reaction conditions, energy saving, and higher purity of the product.
Description
Technical field
The present invention relates to the preparation method of a kind of higher fatty acid magnesium salts that is mainly used in fields such as pharmacy, makeup, plastics, coating industry, tablet vehicle, the makeup adhesion of powder class and lubricant, plastic heat stabilizer and lubricant, the transparent matting agent of coating, calcium salt, strontium salt.
Background technology
The preparation of higher fatty acid polyvalent metal salt mainly contains four kinds of methods at present: double decomposition, scorification, semi-melting method, direct method.Double decomposition is the aqueous solution that adds inorganic metal salt in the aqueous solution of fatty acid sodium salt, replaces sodium ion with inorganic metal ion, again through washing, dry and obtain product; Scorification be fused lipid acid and metal oxide or oxyhydroxide under the temperature more than the melting point of the soap that is generated, be molten state and react and obtain liquid product, behind cooling curing finished product; The semi-melting method be fused lipid acid and metal oxide or oxyhydroxide under the temperature below the melting point of the soap that is generated, being partly, the state of dissolving reacts and directly obtains the solid finished product; Direct method be powdery lipid acid and metal oxide or oxyhydroxide under the high speed dispersion stirring condition, directly form the powdery solid finished product.
Double decomposition produces a large amount of brine wastes in process of production, in being eliminated gradually.Scorification is the good method of producing the lipid acid polyvalent metal salt, and still, because the viscosity of higher fatty acid alkali salt more than fusing point is very big, and it is increasing to press the order of magnesium, calcium, strontium.Powdered metal oxide or oxyhydroxide were difficult to effectively be disperseed in the reaction later stage like this, even under bigger power consumption, also be difficult to carry out equimolar reaction, and color were dark, and hardness is big, were difficult to pulverize.
Direct method, the preparation method of the fatty acid metal salt disclosed in the flat 09-100253 of TOHKEMY.From embodiment as can be seen, with hydrogenated tallow and calcium oxide at normal temperatures, under the stirring velocity with 6.5 meter per seconds-19 meter per second (peripheral speed), be warming up to 100 ℃ stage by stage by normal temperature in 30 minutes, add stearic acid at twice, and remain under this temperature reaction and obtained the purpose product in 60 minutes.This method stirs the linear velocity of powder with average 10 meter per seconds 1.5 hours, and is relatively harsher to the requirement of appointed condition, and bigger power consumption is also arranged simultaneously.
The semi-melting method, the preparation method of the higher fatty acid metal-salt disclosed in the flat 11-35518 of TOHKEMY.From embodiment as can be seen, this method is carried out in two steps for the preparation of alkaline earth metal stearate, at first stearic acid fusing and powdery calcium hydroxide, acetic acid (catalyzer) continuous and quantitative are imported a high-speed mixing decollator, 1000 rev/mins of rotating speeds (outer peripheral lines speed 12 meter per seconds), process 5-10 residence time second discharges continuously, cooling curing is ground into ultra-fine micropowder.Then, in another mixing tank, add the ratio of 7 gram water at twice, stirred altogether 40 minutes and obtain product with 100 gram admixed finepowders.2 difficulties relatively in industrial implementation are arranged in this method, the one, fused liquid stearic acid and solid, powdery calcium hydroxide successive realize moment etc. mol ratio measure, require high-precision metering outfit.The 2nd, the stearic acid mixture that fusing point is lower is ground into ultra-fine micropowder, when summer, needs to carry out under far below the condition of room temperature.Requirement to appointed condition is also relatively harsher.The water that generates with reaction that whether needs to remove especially adding does not in addition offer some clarification in patent.
So, seek that a kind of technology is simple, reaction conditions is gentle, prepare the commercial run of higher fatty acid alkali salt efficiently, be the demand of present industry member.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides that a kind of technology is simple relatively, reaction conditions is gentle, prepare the commercial run of higher fatty acid alkali salt efficiently.
The technical solution adopted for the present invention to solve the technical problems is:
Fused higher fatty acid and micro mist shape alkaline earth metal oxide or oxyhydroxide, through pre-mixing, dispersion, then with the aqueous solution that contains catalyzer, wetting agent, infeed continuously and can control the super mixer of doing time in advance, export to continuously again in the insulation jar, under suitable temperature, keep certain hour, after crushed, can prepare a kind of powdered higher fatty acid alkali salt product.
Higher fatty acid in this programme refers to C
8-C
22Saturated fatty acid, preferable scope is C
12-C
18Saturated fatty acid.If carbon number is especially too fast with the metal hydroxides speed of response with metal oxide or oxyhydroxide less than 8, cause preparation process to carry out smoothly; If carbon number greater than 22, then because activity is too low, and needs to add more catalyzer and auxiliary agent, and influences the purity of product.
Micro mist shape alkaline earth metal oxide in this programme or oxyhydroxide are meant the oxide compound or the oxyhydroxide of magnesium, calcium, strontium, and its size distribution is that 1～50 micron, preferable scope are 2～11 microns.If particle diameter less than 1 micron, when disperseing, easily produces aggregate in fused lipid acid, carry a large amount of air, hindered the abundant contact of two phase materials, the thoroughness of reaction is affected; If particle diameter is greater than 50 microns, the area that contacts obviously reduces, and makes this solid-liquid phase reaction be difficult to carry out thoroughly.The add-on that must make metal oxide or oxyhydroxide just can make free acid value drop in the acceptable ranges much larger than the equivalent ratio.
The mixing temperature of fused higher fatty acid and micro mist shape alkaline earth metal oxide or oxyhydroxide be the molten point of lipid acid to being higher than 30 ℃ of molten points, better temperature range be than molten point high 10 ℃～20 ℃.Because when temperature is higher, the bad stability of mixed system, next step continuous output does not also finish, and just chemical reaction has taken place in part, and makes production to carry out; If mixing temperature is too low, make through the mixed material of super mixer, in insulation jar, do not react for a long time, when accumulation of material when a certain amount of, reaction takes place suddenly, a large amount of materials overflow insulation jar, also make production to carry out.
Employed catalyzer can be an an acidic catalyst in this programme, as organic monoprotic acid, organic dibasic acid or hydrogen peroxide.Organic monoprotic acid can be formic acid, acetate, propionic acid, peroxyformic acid, Peracetic Acid, p-methyl benzenesulfonic acid etc., and organic dibasic acid can be: oxalic acid, propanedioic acid, Succinic Acid, phthalic acid, m-phthalic acid, terephthalic acid etc.; The catalytic activity of p-methyl benzenesulfonic acid and organic dibasic acid is higher; Overall equilbrium toxicity and reactive behavior adopt hydrogen peroxide proper if consider the purity of product, if can be selected formic acid, acetate, propionic acid, peroxyformic acid, Peracetic Acid for use.Its add-on is 0.01%～1% of a lipid acid dispersion thing, preferable add-on 0.05%～0.5%.If add-on less than 0.01% o'clock, above-mentioned fusion higher fatty acid and the too low phenomenon of electrodeless micro mist mixing temperature can occur; If add-on is greater than 1%, because speed of response is too fast, fully just intense reaction takes place with the lipid acid dispersion is also unmixed in super mixer, still cause reaction not thorough.In addition, the clean-up performance of product is descended.
Employed wetting agent can be anion surfactant, nonionogenic tenside or its mixture in this programme.Anion surfactant can comprise sodium laurate, potassium laurate, sodium lauryl sulphate (K-12), Sodium dodecylbenzene sulfonate (LAS), diisooctyl alcohol succinate sodium sulfonate (permeate agent OT), ethoxylated dodecyl alcohol sodium sulfonate (or ammonium salt) (AES), polyoxyethylene nonylphenol ether sodium sulfonate (or ammonium salt) etc.; Nonionogenic tenside can comprise isooctyl alcohol Soxylat A 25-7 (penetrating agent JFC), lauryl alcohol Soxylat A 25-7 (LEO-5, LEO-9), polyoxyethylene nonylphenol ether (NP-7, NP-10) etc.Consider validity and toxicity, preferable selection is sodium laurate, potassium laurate, K-12, OT, JFC, LEO-5 etc.Add-on is for for lipid acid disperses 0.05%～1% of thing, if add-on is lower than 0.05%, the inorganic micro powder reaction not exclusively causes the product free acid higher; If add-on is higher than 1%, then the clean-up performance of product descends.
The super mixer that the control of being adopted in this programme is done time in advance is the mixing tank of back taper bodily form energy control volume internal rotor speed, the rotating speed difference of its rotor, give different centrifugal force for the material that enters, this centrifugal action produces a kind of thrust of rising in the reverse taper wall to material, contend with the gravity that descends, rotating speed is fast more, and centrifugal force is big more, and rising thrust is big more, the input and output inventory slows down, the premix time lengthening.According to the processing requirement of different material, to control different mixing times and discharging speed.Do time in advance and can be controlled at 5 seconds～35 seconds.
The insulation jar that is adopted in this programme, no whipping appts, holding temperature is controlled at 70 ℃～110 ℃, and preferable temperature range is 80 ℃～100 ℃.If temperature is lower than 70 ℃, react not thorough; If be higher than 110 ℃, then the initial stage of product formation cured article in jar, its fusing point is lower, makes to be affixed on the at first fusion of tank skin product, and along with the carrying out of reaction, fusing point raises gradually, and the scleroid product of last easily formation is difficult to be ground into trickle powder.And the product color has the xanthochromia tendency.Soaking time 1～4 hour.
The pulverizer that is adopted in this programme can adopt common mechanical disintegration to add the whirlwind tripping device, and median size can be controlled at 5～20 microns, has removed most of moisture content in the process of pulverizing, and makes weight loss on heating≤3% of product.(calcium stearate: the industry standard HG/T2424-93 of the Ministry of Chemical Industry, weight loss on heating≤3%; Magnesium Stearate: pharmacopeia 2005 editions, weight loss on heating≤5%).
The invention has the beneficial effects as follows: (1), fused higher fatty acid and micro mist shape alkaline earth metal oxide or oxyhydroxide carry out pre-mixing, dispersion under the situation that does not add catalyzer and any auxiliary agent.Metering is simplified,, be unlikely producing tangible chemical reaction owing to do not add catalyzer and any auxiliary agent thereby guaranteed system stability in pre-mixing, the dispersion process.(2), catalyzer, wetting agent infeed continuously with the form of the aqueous solution and molten fat acid dispersion liquid passing ratio pump and can control the super mixer of doing time in advance, this process also is that metering is simplified, the more important thing is because the adding of wetting agent guarantees that aqueous catalyst solution is quick in molten fat acid dispersion, efficiently disperses, make in the molten fat acid dispersive inorganic micro powder realize that secondary disperses simultaneously, for the adequacy of heterogeneous reaction provides safeguard.(3), the material in the super mixer exports in the insulation jar continuously, be reflected to need not to finish under the stirring condition.This step has guaranteed continuity, the simplicity of process.(4), pass through the mechanical disintegration process, removing moisture content when obtaining powdered product.Thereby the energy saving of the process of assurance.Whole process of preparation technology is simple, equipment is simple, reaction conditions is gentle, save the energy; And product purity is higher.
The present invention is further described below in conjunction with embodiment.
Embodiment
Embodiment 1: the preparation method of Magnesium Stearate
100 kilograms of stearic acid (acid number 210), be heated to 80 ℃, add 8.2 kilograms of magnesium oxide (96%) micro mists, pre-mixing, dispersion are then with the aqueous solution 20kg that contains catalyzer (acetate 0.06kg), wetting agent (sodium lauryl sulphate 0.12kg) that is preheating to 80 ℃ in advance, infeed continuously and can control the super mixer of doing time in advance, did time in advance about 20 seconds, and exported to continuously then in the insulation jar that has been preheating to 80～90 ℃, be incubated 2 hours, after crushed, promptly obtain the purpose product.Its quality index is: content of magnesia 7.5%, free acid≤1%, weight loss on heating≤3%, fusing point 〉=120 ℃, fineness≤75 μ m.
Annotate: the stearic acid that uses in the present embodiment (acid number 210) is the mixing acid of 16 carbonic acid contents 60%, 18 carbonic acid contents 40%, so metal content is more higher than standard.Down together.
Embodiment 2: the preparation method of Magnesium Stearate
100 kilograms of stearic acid (acid number 210), be heated to 80 ℃, add 11.5 kilograms of magnesium hydroxide (98%) micro mists, pre-mixing, dispersion are then with the aqueous solution 20kg that contains catalyzer (hydrogen peroxide 0.2kg), wetting agent (potassium laurate 0.12kg) that is preheating to 80 ℃ in advance, infeed continuously and can control the super mixer of doing time in advance, did time in advance about 15 seconds, and exported to continuously then in the insulation jar that has been preheating to 80～90 ℃, be incubated 2 hours, after crushed, promptly obtain the purpose product.Its quality index is: content of magnesia 7.5%, free acid≤1%, weight loss on heating≤3%, fusing point 〉=120 ℃, fineness≤75 μ m.
Embodiment 3: the preparation method of calcium stearate
100 kilograms of stearic acid (acid number 210), be heated to 75 ℃, add 12.1 kilograms of calcium oxide (89%) micro mists, pre-mixing, dispersion, then with the aqueous solution 20kg that contains catalyzer (p-methyl benzenesulfonic acid 0.04kg), wetting agent (diisooctyl alcohol succinate sodium sulfonate 0.06kg) that is preheating to 80 ℃ in advance, infeed continuously and can control the super mixer of doing time in advance, did time in advance about 15 seconds, export to continuously then in the insulation jar that has been preheating to 80～90 ℃, be incubated 2 hours, after crushed, promptly obtain the purpose product.Its quality index is: calcium contents 7.0%, free acid≤1%, weight loss on heating≤3%, fusing point 〉=150 ℃, fineness≤75 μ m.
Embodiment 4: the preparation method of calcium stearate
100 kilograms of stearic acid (acid number 210), be heated to 70 ℃, add 12.1 kilograms of calcium hydroxide (96%) micro mists, pre-mixing, dispersion are then with the aqueous solution 20kg that contains catalyzer (acetate 0.06kg), wetting agent (sodium lauryl sulphate 0.12kg) that is preheating to 80 ℃ in advance, infeed continuously and can control the super mixer of doing time in advance, did time in advance about 10 seconds, and exported to continuously then in the insulation jar that has been preheating to 80～900 ℃, be incubated 2 hours, after crushed, promptly obtain the purpose product.Its quality index is: calcium contents 7.0%, free acid≤1%, weight loss on heating≤3%, fusing point 〉=150 ℃, fineness≤75 μ m.
Subordinate list: the quality index of Magnesium Stearate in calcium stearate and the pharmacopeia 2005 editions among the HG/T2424-93
Table 1: calcium stearate
Table 2: Magnesium Stearate
| Outward appearance | Content of magnesia % | Weight loss on drying % | Vitriol % | Muriate % | Molysite % | Heavy metal % |
| White fine powder | 6.5～7.5 | ≤5.0 | ≤0.6 | ≤0.15 | ≤ 0.01 | ≤.0001 |
。
Claims (10)
1. the preparation method of a higher fatty acid alkali salt, it is characterized in that this preparation method is with fused higher fatty acid and micro mist shape alkaline earth metal oxide or oxyhydroxide, through pre-mixing, dispersion, then with the aqueous solution that contains catalyzer, wetting agent, infeed continuously and can control the super mixer of doing time in advance, export to continuously again in the insulation jar, under 70 ℃～110 ℃ temperature, kept 1～4 hour, after crushed, promptly prepare a kind of powdered higher fatty acid alkali salt.
2. the preparation method of a kind of higher fatty acid alkali salt according to claim 1 is characterized in that higher fatty acid is C
8-C
22Saturated fatty acid.
3. the preparation method of a kind of higher fatty acid alkali salt according to claim 1 is characterized in that higher fatty acid is C
12-C
18Saturated fatty acid.
4. the preparation method of a kind of higher fatty acid alkali salt according to claim 1 is characterized in that micro mist shape alkaline earth metal oxide or oxyhydroxide are meant the oxide compound or the oxyhydroxide of magnesium, calcium, strontium, and its size distribution is 1～50 micron.
5. the preparation method of a kind of higher fatty acid alkali salt according to claim 1 is characterized in that the oxide compound of magnesium, calcium, strontium or the particle size distribution range of oxyhydroxide are 2～10 microns.
6. the preparation method of a kind of higher fatty acid alkali salt according to claim 1 is characterized in that the organic monoprotic acid of described catalyzer, organic dibasic acid or hydrogen peroxide.
7. the preparation method of a kind of higher fatty acid alkali salt according to claim 6 is characterized in that organic monoprotic acid is a kind of in formic acid, acetate, propionic acid, peroxyformic acid, Peracetic Acid, the p-methyl benzenesulfonic acid; Organic dibasic acid is a kind of in oxalic acid, propanedioic acid, Succinic Acid, phthalic acid, m-phthalic acid, the terephthalic acid.
8. the preparation method of a kind of higher fatty acid alkali salt according to claim 1 is characterized in that described wetting agent can be anion surfactant, nonionogenic tenside or its mixture.
9. the preparation method of a kind of higher fatty acid alkali salt according to claim 8 is characterized in that described anion surfactant is a kind of in sodium laurate, potassium laurate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, diisooctyl alcohol succinate sodium sulfonate, ethoxylated dodecyl alcohol sodium sulfonate, ethoxylated dodecyl alcohol sulfonic acid ammonium salt, polyoxyethylene nonylphenol ether sodium sulfonate, the polyoxyethylene nonylphenol ether sulfonic acid ammonium salt; Described nonionogenic tenside is a kind of in octyl group polyoxyethylenated alcohol, lauryl alcohol Soxylat A 25-7, the polyoxyethylene nonylphenol ether.
10. the preparation method of a kind of higher fatty acid alkali salt according to claim 1, it is characterized in that controlling the super mixer of doing time in advance is the mixing tank of back taper bodily form energy control volume internal rotor speed, the rotating speed difference of its rotor, give different rising component for the material that enters, according to the processing requirement of different material, to control different mixing times and discharging speed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100300829A CN101337877B (en) | 2008-08-07 | 2008-08-07 | Method for preparing higher fatty acid alkali salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100300829A CN101337877B (en) | 2008-08-07 | 2008-08-07 | Method for preparing higher fatty acid alkali salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101337877A true CN101337877A (en) | 2009-01-07 |
| CN101337877B CN101337877B (en) | 2011-05-25 |
Family
ID=40212069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100300829A Active CN101337877B (en) | 2008-08-07 | 2008-08-07 | Method for preparing higher fatty acid alkali salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101337877B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864699A (en) * | 2010-06-29 | 2010-10-20 | 上海东升新材料有限公司 | Method for preparing calcium stearate lubricant for papermaking |
| CN102219667A (en) * | 2011-04-22 | 2011-10-19 | 中山市华明泰化工材料科技有限公司 | Higher fatty acid metal salt and preparation method thereof |
| CN102924260A (en) * | 2012-10-29 | 2013-02-13 | 杭州油脂化工有限公司 | Technique and device for continuously producing stearate by low-temperature dry process |
| CN103450003A (en) * | 2013-09-18 | 2013-12-18 | 南通新邦化工科技有限公司 | Preparation process of lead stearate based on melting method |
| CN103524324A (en) * | 2013-09-22 | 2014-01-22 | 南通新邦化工科技有限公司 | Method for preparing magnesium stearate by normal-pressure melting |
| CN104003864A (en) * | 2014-06-09 | 2014-08-27 | 广东信诚达科技有限公司 | Fatty acid alkaline-earth metal salt and preparation method thereof |
| CN110386871A (en) * | 2019-08-27 | 2019-10-29 | 如皋市涤诺皂业有限公司 | A kind of production technology of magnesium stearate |
| CN111848389A (en) * | 2020-08-20 | 2020-10-30 | 中山华明泰科技股份有限公司 | Preparation method and application of palm oil fatty acid magnesium |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6392075B1 (en) * | 2000-09-29 | 2002-05-21 | Norel Acquisition Corp. | Method for manufacturing calcium salts of highly unsaturated fatty acids |
| CN100339349C (en) * | 2004-09-22 | 2007-09-26 | 内蒙古自治区畜牧科学院 | Preparation method of long chain fatty acid calcium salt |
| ES2249995B1 (en) * | 2004-09-22 | 2007-06-01 | Norel, S.A. | PROCEDURE FOR THE PRODUCTION OF CALCICAL, SODIUM OR MAGNESIC SOAPS OF FATTY ACIDS OR OLEINS OF VEGETABLE OR ANIMAL FATS AND THEIR USE AS NUTRIENTS IN FOOD OF MONOGASTRIC ANIMALS. |
| CN100580179C (en) * | 2007-12-24 | 2010-01-13 | 上海东升新材料有限公司 | Preparing method of calcium stearate lubricating agent for making paper |
-
2008
- 2008-08-07 CN CN2008100300829A patent/CN101337877B/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864699A (en) * | 2010-06-29 | 2010-10-20 | 上海东升新材料有限公司 | Method for preparing calcium stearate lubricant for papermaking |
| CN102219667A (en) * | 2011-04-22 | 2011-10-19 | 中山市华明泰化工材料科技有限公司 | Higher fatty acid metal salt and preparation method thereof |
| CN102924260A (en) * | 2012-10-29 | 2013-02-13 | 杭州油脂化工有限公司 | Technique and device for continuously producing stearate by low-temperature dry process |
| CN102924260B (en) * | 2012-10-29 | 2015-03-18 | 杭州油脂化工有限公司 | Technique and device for continuously producing stearate by low-temperature dry process |
| CN103450003A (en) * | 2013-09-18 | 2013-12-18 | 南通新邦化工科技有限公司 | Preparation process of lead stearate based on melting method |
| CN103524324A (en) * | 2013-09-22 | 2014-01-22 | 南通新邦化工科技有限公司 | Method for preparing magnesium stearate by normal-pressure melting |
| CN104003864A (en) * | 2014-06-09 | 2014-08-27 | 广东信诚达科技有限公司 | Fatty acid alkaline-earth metal salt and preparation method thereof |
| CN110386871A (en) * | 2019-08-27 | 2019-10-29 | 如皋市涤诺皂业有限公司 | A kind of production technology of magnesium stearate |
| CN111848389A (en) * | 2020-08-20 | 2020-10-30 | 中山华明泰科技股份有限公司 | Preparation method and application of palm oil fatty acid magnesium |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101337877B (en) | 2011-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101337877B (en) | Method for preparing higher fatty acid alkali salt | |
| US5318733A (en) | Production of compacted granules for detergents | |
| KR101072911B1 (en) | - powders flakes or pellets containing salts of -sulfofatty acid alkyl esters in high concentrations process for production thereof granulated detergents and process for production thereof | |
| CN104741244B (en) | Silicon-calcium collophanite normal-temperature direct flotation collecting agent and preparation method thereof | |
| CN101955855A (en) | Spheroidal detergent composition and preparation method thereof | |
| CN100427398C (en) | Method for preparing nanometer calcium carbonate | |
| CN101440331B (en) | Composition for detergent and use thereof | |
| CN101001942A (en) | Process for making a granular detergent composition having improved solubility | |
| CN103044233A (en) | Process for preparing stearate through ball milling | |
| CN102604760A (en) | Low-temperature instant soap powder and preparation method thereof | |
| CN104261986A (en) | Chemical fertilizer anti-caking agent prepared from hydrogenated drainage oil | |
| TW517080B (en) | Process for preparing high bulk density detergent compositions | |
| CN103320235A (en) | Particles containing sodium fatty acid methyl ester sulfonate and preparation method thereof | |
| CN101743300A (en) | Method for producing anionic surfactant powder particle | |
| ZA200207293B (en) | Process for preparing fluid detergent compositions. | |
| CN102094208A (en) | Environmental-friendly low-foam degreasing powder for surface cleaning of steel materials and preparation method thereof | |
| CN107189888A (en) | It is a kind of to add the method that camellia seed oil prepares handmade soap | |
| CN106811330A (en) | One kind laundry effervescent tablet and preparation method thereof | |
| CN106928603B (en) | Emulsify calcium stearate pulvis and its preparation and application | |
| JP2011127106A (en) | Method for producing detergent granule cluster | |
| CN104726168A (en) | Lithium-zinc compound lubricant and preparation method thereof | |
| CN109965105A (en) | A kind of production technology of feed grade liquid natural lutein product | |
| CN107840788A (en) | A kind of preparation method of lithium 12-hydroxy stearate | |
| CN103396272A (en) | Method for recycling waste emulsion explosive in rock powder emulsion explosive | |
| CN102746727B (en) | Preparation method of water-based wood lacquer polishing agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: ZHONGSHAN CITY HUAMINGTAI CHEMICAL MATERIAL TECHNO Free format text: FORMER OWNER: BAILIHE CHEMICAL (ZHONGSHAN) CO., LTD. Effective date: 20100820 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20100820 Address after: 528441, Sha town, Guangdong City, Zhongshan Province Sha Tsai Industrial Park Applicant after: ZHONGSHAN HUAMINGTAI CHEMICAL MATERIAL TECHNOLOGY Co.,Ltd. Address before: 528441, Sha town, Guangdong City, Zhongshan Province Sha Tsai Industrial Park Applicant before: BAILIHE CHEMICAL (ZHONGSHAN) Co.,Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 702, 12, investment building, 528437 East Conference Road, Torch Development Zone, Guangdong, Zhongshan Patentee after: ZHONGSHAN HUAMINGTAI TECHNOLOGY CO.,LTD. Address before: 702, 12, investment building, 528441 East Conference Road, Torch Development Zone, Guangdong, Zhongshan Patentee before: BELIKE CHEMICAL Co.,Ltd. Address after: 702, 12, investment building, 528441 East Conference Road, Torch Development Zone, Guangdong, Zhongshan Patentee after: BELIKE CHEMICAL Co.,Ltd. Address before: 528441, Sha town, Guangdong City, Zhongshan Province Sha Tsai Industrial Park Patentee before: Zhongshan Huamingtai Chemical Material Technology Co.,Ltd. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for preparing higher fatty acid alkali salt Effective date of registration: 20180410 Granted publication date: 20110525 Pledgee: China Co. truction Bank Corp Zhongshan branch Pledgor: ZHONGSHAN HUAMINGTAI TECHNOLOGY CO.,LTD. Registration number: 2018990000281 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20210316 Granted publication date: 20110525 Pledgee: China Co. truction Bank Corp Zhongshan branch Pledgor: ZHONGSHAN HUAMINGTAI TECHNOLOGY Co.,Ltd. Registration number: 2018990000281 |