CN1116371C - Method for preparing drier - Google Patents
Method for preparing drier Download PDFInfo
- Publication number
- CN1116371C CN1116371C CN00110821A CN00110821A CN1116371C CN 1116371 C CN1116371 C CN 1116371C CN 00110821 A CN00110821 A CN 00110821A CN 00110821 A CN00110821 A CN 00110821A CN 1116371 C CN1116371 C CN 1116371C
- Authority
- CN
- China
- Prior art keywords
- carboxylic acid
- low molecular
- entrainer
- water
- azeotrope
- 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.)
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Links
- 238000000034 method Methods 0.000 title abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- -1 C20 fatty acids Chemical class 0.000 claims abstract description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 146
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 60
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 150000001734 carboxylic acid salts Chemical class 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 2
- 229930195729 fatty acid Natural products 0.000 abstract description 2
- 239000000194 fatty acid Substances 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 6
- 150000007942 carboxylates Chemical class 0.000 abstract 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 22
- 239000000047 product Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 14
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 10
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- 239000012141 concentrate Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 235000009328 Amaranthus caudatus Nutrition 0.000 description 4
- 240000001592 Amaranthus caudatus Species 0.000 description 4
- 235000012735 amaranth Nutrition 0.000 description 4
- 239000004178 amaranth Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- FUPMSLTYEIZSLZ-UHFFFAOYSA-N cobalt;naphthalene-1-carboxylic acid Chemical compound [Co].C1=CC=C2C(C(=O)O)=CC=CC2=C1 FUPMSLTYEIZSLZ-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- TZWGXFOSKIHUPW-UHFFFAOYSA-L cobalt(2+);propanoate Chemical compound [Co+2].CCC([O-])=O.CCC([O-])=O TZWGXFOSKIHUPW-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for preparing a drier. In the method, the low molecular carboxylate of a metal iron M<n+> or a water solution of the metal iron M<n+> and C8 to C20 fatty acids or an aromatic carboxylic acid directly react; in the reaction process, an entrainer is added for dewatering, and a low molecular carboxylic acid generated in reaction is separated; water and the low molecular carboxylic acid separated in the reaction process are recovered and then are used for preparing a low molecular carboxylate of a metal iron; a recovered entrainer or an azeotrope of the entrainer with the low molecular carboxylic acid can be recycled in the preparation process of a drier. The method can shorten a technological process, improve the conversion rate of M <n+>, improve the quality of a product and reduce or completely eliminate waste water discharge.
Description
The invention belongs to preparation method, a kind of metal ions M of using of saying so in more detail as the compound of siccative
N+C
2-C
4Low molecular carboxylic acid salt and C
8-C
20Aliphatics or aromatic carboxylic acid direct production compound (M
N+) (Y
-)
nMethod.
U.S. Pat 3332971 discloses a kind of siccative--and the manufacture method of cobalt iso-octoate or naphthoic acid cobalt, this method are that an alkali metal salt with Cobaltous diacetate or Cobaltous propionate and isocaprylic acid or naphthoic acid reacts synthetic cobalt iso-octoate or naphthoic acid cobalt siccative in the presence of inert solvent.There is following disadvantage in this method, and the one, the reaction process complexity must at first be converted into an alkali metal salt etc. with the long-chain carboxylic acid; The 2nd, to carry out carrying out washing treatment with refining to reaction product; The 3rd, can produce a large amount of brine wastes in process of production, as unreasonable processing, with contaminate environment.
Purpose of the present invention is exactly a kind of preparation method of siccative, and this method has overcome above-mentioned shortcoming of the prior art, adopts new technology, can shorten compound (M
N+Y
- n) the technological process of production, improve M
N+Transformation efficiency, improve the quality of products, reduce or eliminate discharge of wastewater fully.
The objective of the invention is to realize by the following technical solutions: by metal ions M
N+Low molecular carboxylic acid salt M
N+X
- n(M is that Co, Mn, Pb, Fe, Zn, Zr, Ce, Ni, Cu, Ca, K etc. can form a kind of in the metal of low molecular carboxylic acid salt here; N is 1,2,3,4 or 5; X is C
2-C
4Low molecular carboxylic acid) or its aqueous solution and C
8-C
20Aliphatics or aromatic carboxylic acid directly react with stoichiometric ratio, and in reaction process, add the low molecular carboxylic acid that entrainer dewaters and (perhaps) further separation removal reaction produces, reclaim and recycle reacting the low molecular carboxylic acid, the entrainer of recovery or the azeotrope and the water of entrainer and low molecular carboxylic acid that produce.
Stoichiometric equation of chemical reaction of the present invention is: (s represents solid, and l represents liquid, and g represents gas)
(M
n+)(X
-)
n+nY(l)＝(M
n+)(Y
-)
n(l)+X(g)
Wherein: Y is C
8-C
20Aliphatics or aromatic carboxylic acid, other is the same.
Metal ions M in the present invention
N+C
8-C
20The preparation of carboxylate salt siccative is by metal ions M
N+Low molecular carboxylic acid salt or its aqueous solution and C
8-C
20Carboxylic acid directly react.Its reaction principle is characteristics such as lower than long carbochain carboxylic acid boiling point by low molecular carboxylic acid, volatile, constantly will react the low molecular carboxylic acid that generates and discharge reaction system in reaction process, promotes reaction to carry out to helping the direction that siccative forms.In the present invention, work as metal ions M
N+Low molecular carboxylic acid salt when participating in reaction with solid form, before the reaction beginning with entrainer and C
8-C
20Carboxylic acid add simultaneously; When participating in reaction with aqueous solution form as the low molecular carboxylic acid salt of reactant, reclaim and reduce the entrainer pollution effect as far as possible for convenient, at first solution is concentrated, when the concentrated solution thickness or when having solid to separate out, add its boil agent and C again
8-C
20Carboxylic acid, remove water in the reactive system by entrainer, when no longer including the water discharge, steam the azeotrope of entrainer or entrainer and low molecular carboxylic acid, the last low molecular carboxylic acid that removes the reaction generation fully, the reactor residuum is the solvent-free siccative that will prepare, and contains solvent siccative product according to what different needs added therein that appropriate solvent can obtain different solvents, different concns.
The selection principle of entrainer is that entrainer can form azeotrope with water, and do not form azeotrope with carboxylic acid, perhaps in the azeotrope composition that entrainer and low molecular carboxylic acid form, low molecular carboxylic acid is occupied less mark, maximum is no more than 50% (weight percent), in the azeotrope of entrainer and low molecular carboxylic acid formation, the ratio of carboxylic acid is too high, as surpassing 50%, can increase general facilities and recovery cost, reduce working efficiency, in the present invention, select benzene, toluene, vinyl acetic monomer, N-BUTYL ACETATE, propyl acetate, hydrochloric ether, ether etc. are for meeting the entrainer of above-mentioned requirements.
The reaction azeotropic temperature is variant with the difference of selected entrainer among the present invention.When removing low molecular carboxylic acid, improve temperature of reaction and help accelerating and removing low molecular carboxylic acid fully, but in order to prevent C
8-C
20Carboxylic acid and M
N+Siccative (the M that forms
N+Y
- n) at high temperature decompose, influence quality product, the outlet temperature of reaction mass generally should be lower than the long-chain carboxylic acid's boiling point of using more than 30 ℃, be preferably in more than 50 ℃.
For the water of telling in the reaction process, low molecular carboxylic acid, can be used for preparing the low molecular carboxylic acid salt of metal ion after the recovery.The entrainer that reclaims or the azeotrope of entrainer and low molecular carboxylic acid can be recycled in the siccative manufacturing processed.
Below by embodiment the present invention is described in further detail:
Embodiment 1, and in a reactor that has whipping appts, thermometer, a division box, [chemical formula is: Co (CH to add 400 gram concentration and be the Cobaltous diacetate of 11.80% (by weight percentage)
3COO)
24H
2O] the aqueous solution, heating concentrates, when minute aquifer yield is 321 milliliters, add 55.7 gram isocaprylic acid and 40ml benzene, and further remove water in the reaction system by water trap, when water in the water trap slightly becomes muddy, the conversion receptor, between 80-85 ℃, collect the azeotrope of benzene and acetic acid, in 116-120 ℃ of scope, collect acetic acid again, when temperature of charge in the reactor rose to 160 ℃, reaction mass all was the oiliness state, keep temperature of reaction at 160-170 ℃ till no acetic acid steams, the cobalt iso-octoate that obtains is the amaranth thick liquid, become semisolid after the cooling, as thinner, the siccative quality product that obtains meets the HG2276-92 standard with gasoline or N-BUTYL ACETATE.Azeotrope, the acetic acid of isolated water, benzene and acetic acid can be recycled.
Embodiment 2, have whipping appts at one, temperature is taken into account in the reactor of division box, and [chemical formula is: Mn (CH to add 47 gram purity and be 98% four water acetic acid manganese
3COO)
24H
2O] crystal, 55.7 gram isocaprylic acid and 40 milliliters of benzene, reacting by heating, and remove water in the reaction system by water trap, when water in the water trap slightly becomes muddy, the conversion receptor, between 80-85 ℃, collect the azeotrope of benzene and acetic acid, in 116-120 ℃ of scope, collect acetic acid again, when temperature of charge in the reactor rises to 160 ℃, reaction mass all is the oiliness state, keep temperature of reaction 160-170 ℃ till no acetic acid steams, the manganese iso-octoate that obtains becomes semisolid after the cooling, as thinner, the siccative quality product that obtains meets the HG2276-92 standard with gasoline or N-BUTYL ACETATE.Azeotrope, the acetic acid of isolated water, benzene and acetic acid can be recycled.
Embodiment 3, have whipping appts at one, temperature is taken into account in the reactor of division box, adding 60 gram acid numbers is the naphthenic acid of 156 milligrams of KOH/ grams, purity is Cobaltous diacetate crystal 2 1.2 gram and 45 milliliters of benzene of 98.2%, reacting by heating, other is with example 1, and it is thick that the product that obtains is dark purple brown, obtaining containing cobalt with No. 200 gasoline dilutions is 4% band solvent siccative product, and quality meets the HG2276-92 standard.
Embodiment 4, have whipping appts at one, temperature is taken into account in the reactor of division box, the adding cobalt contents is 2.1% the cobaltous butyrate aqueous solution 400 grams, heating concentrates, when treating that the branch aquifer yield reaches 300 milliliters, adding acid number is the naphthenic acid of 156 milligrams of KOH/ grams, 102.4 gram and 40 milliliters of benzene, reacting by heating, and further remove the water of reaction system by water trap, when water begins to become muddiness in the water trap, the conversion receptor is collected benzene between 80-120 ℃, be that 200-220 ℃ scope is a 140-144 ℃ of butyric acid cut for collecting boiling range in the reaction mass temperature after this, when no butyric acid is told, the cobalt naphthenate that obtains is dark purple brown thick liquid, and obtaining containing cobalt with the dilution of No. 200 gasoline is 4% band solvent siccative product, its quality conformance with standard HG2276-92.Azeotrope, the acetic acid of isolated water, benzene and acetic acid can be recycled.
Embodiment 5, and in a reactor that has whipping appts, thermometer, a division box, [chemical formula is: Co (CH to add 400 gram concentration and be the Cobaltous diacetate of 11.80% (by weight percentage)
3COO)
24H
2O] the aqueous solution, heating concentrates, when minute aquifer yield is 321 milliliters, add 55.7 gram isocaprylic acid and 50 milliliters of chlorobenzenes, and further remove water in the reaction system by water trap, when water in the water trap slightly becomes muddy, the conversion receptor, at the azeotrope of collecting chlorobenzene and acetic acid below 115 ℃, in 116-120 ℃ of scope, collect acetic acid again, when temperature of charge in the reactor rose to 160 ℃, reaction mass all was the oiliness state, keep temperature of reaction at 160-170 ℃ till no acetic acid steams, the cobalt iso-octoate that obtains is the amaranth thick liquid, become semisolid after the cooling, as thinner, the siccative quality product that obtains meets the HG2276-92 standard with gasoline or N-BUTYL ACETATE.Azeotrope, the acetic acid of isolated water, chlorobenzene and acetic acid can be recycled.
Embodiment 6, and in a reactor that has whipping appts, thermometer, a division box, [chemical formula is: Co (CH to add 400 gram concentration and be the Cobaltous diacetate of 11.80% (by weight percentage)
3COO)
24H
2O] the aqueous solution, heating concentrates, when minute aquifer yield is 321 milliliters, add 55.7 gram isocaprylic acid and 45ml toluene, and further remove water in the reaction system by water trap, when water in the water trap slightly becomes muddy, the conversion receptor, at the azeotrope of collecting toluene and acetic acid below 117 ℃, in 117-120 ℃ of scope, collect acetic acid again, when temperature of charge in the reactor rose to 160 ℃, reaction mass all was the oiliness state, keep temperature of reaction at 160-170 ℃ till no acetic acid steams, the cobalt iso-octoate that obtains is the amaranth thick liquid, become semisolid after the cooling, as thinner, the siccative quality product that obtains meets the HG2276-92 standard with gasoline or N-BUTYL ACETATE.Azeotrope, the acetic acid of isolated water, toluene and acetic acid can be recycled.
Embodiment 7, and in a reactor that has whipping appts, thermometer, a division box, [chemical formula is: Co (CH to add 400 gram concentration and be the Cobaltous diacetate of 11.80% (by weight percentage)
3COO)
24H
2O] the aqueous solution, heating concentrates, when minute aquifer yield is 321 milliliters, add 55.7 gram isocaprylic acid and 50 milliliters of m-xylenes, and further remove water in the reaction system, when water in the water trap slightly becomes muddy by water trap, the conversion receptor, at the azeotrope of collecting m-xylene and acetic acid below 116 ℃, in 116-120 ℃ of scope, collect acetic acid again, other day example 1.Azeotrope, the acetic acid of isolated water, m-xylene and acetic acid can be recycled.
Embodiment 8, and in a reactor that has whipping appts, thermometer, a division box, [chemical formula is: Co (CH to add 400 gram concentration and be the Cobaltous diacetate of 11.80% (by weight percentage)
3COO)
24H
2O] the aqueous solution, heating concentrates, when minute aquifer yield is 321 milliliters, add 55.7 gram isocaprylic acid and 50 milliliters of ether, and further remove water in the reaction system by water trap, when water in the water trap slightly becomes muddy, the conversion receptor, collecting ether and low-boiling-point substance below 115 ℃, in 116-120 ℃ of scope, collect acetic acid again, when temperature of charge in the reactor rose to 160 ℃, reaction mass all was the oiliness state, keep temperature of reaction at 160-170 ℃ till no acetic acid steams, the cobalt iso-octoate that obtains is the amaranth thick liquid, become semisolid after the cooling, as thinner, the siccative quality product that obtains meets the HG2276-92 standard with gasoline or N-BUTYL ACETATE.Isolated water, ether and low-boiling-point substance, acetic acid can be recycled.
Embodiment 9, and in a reactor that has whipping appts, thermometer, a division box, [chemical formula is: Co (CH to add 400 gram concentration and be the Cobaltous diacetate of 11.80% (by weight percentage)
3COO)
24H
2O] the aqueous solution, heating concentrates, when minute aquifer yield is 321 milliliters, the vinyl acetic monomer that adds 55.7 gram isocaprylic acids and 40 milliliters, and further remove water in the reaction system by water trap, when water in the water trap slightly becomes muddy, the conversion receptor, at the azeotrope of collecting vinyl acetic monomer and acetic acid below 80 ℃, in 116-120 ℃ of scope, collect acetic acid again, as follows embodiment 1.Azeotrope, the acetic acid of isolated water, vinyl acetic monomer and acetic acid can be recycled.
Embodiment 10, and in a reactor that has whipping appts, thermometer, a division box, [chemical formula is: Co (CH to add 400 gram concentration and be the Cobaltous diacetate of 11.80% (by weight percentage)
3COO)
24H
2O] the aqueous solution, heating concentrates, when minute aquifer yield is 321 milliliters, add 55.7 gram isocaprylic acid and 50 milliliters of N-BUTYL ACETATEs, and further remove water in the reaction system, when water in the water trap slightly becomes muddy by water trap, the conversion receptor, at the azeotrope of collecting N-BUTYL ACETATE and water below 93 ℃, in 116-120 ℃ of scope, collect acetic acid again, as follows embodiment 1.Azeotrope, the acetic acid of isolated water, N-BUTYL ACETATE and water can be recycled.
Embodiment 11, and in a reactor that has whipping appts, thermometer, a division box, [chemical formula is: Pb (CH to add 73.1 gram concentration and be the acetate trihydrate lead of 98% (by weight percentage)
3COO)
23H
2O] solid, add 55.7 gram isocaprylic acid and 45 milliliters of benzene, reacting by heating, and remove water in the reaction system by water trap, when water in the water trap slightly becomes muddy, the conversion receptor, between 80-85 ℃, collect the azeotrope of benzene and acetic acid, collect acetic acid again in 116-120 ℃ of scope, when temperature of charge in the reactor rose to 160 ℃, reaction mass all was the oiliness state, keep temperature of reaction at 160-170 ℃ till no acetic acid steams, become semisolid after the plumbous cooling of the isocaprylic acid that obtains, as thinner, the siccative quality product that obtains meets the HG2276-92 standard with gasoline or N-BUTYL ACETATE.Azeotrope, the acetic acid of isolated water, benzene and acetic acid can be recycled.
Embodiment 12, have whipping appts at one, thermometer, in the reactor of division box, add 400 ml concns and count the aqueous solution of 13.2% (by weight percentage) with four acetic acid zirconiums, heating concentrates, when minute aquifer yield is 250 milliliters, add 47.0 gram isocaprylic acid and 45ml benzene, and further remove water in the reaction system by water trap, when water in the water trap slightly becomes muddy, the conversion receptor, the azeotrope of collection benzene and acetic acid is collected acetic acid again in 116-120 ℃ of scope between 80-85 ℃, when temperature of charge in the reactor rises to 160 ℃, reaction mass all is the oiliness state, keep temperature of reaction 160-170 ℃ till no acetic acid steams, become semisolid after the cooling, with gasoline or N-BUTYL ACETATE as thinner, the zirconium iso-octoate siccative quality product conformance with standard that obtains.Azeotrope, the acetic acid of isolated water, benzene and acetic acid can be recycled.
Embodiment 13, have whipping appts at one, temperature is taken into account in the reactor of division box, add 48 gram purity and be 98.2% Cobaltous diacetate crystal, add 55.7 gram isocaprylic acid and 40ml benzene, reacting by heating, and other is as embodiment 1.The siccative quality product that obtains meets the HG2276-92 standard.Azeotrope, the acetic acid of isolated water, benzene and acetic acid can be recycled.
As can be seen from the above embodiments, the present invention has the following advantages.
1, directly adopt longer chain fatty acid or aromatic carboxylic acid to react, reduced the saponification process, it is few to introduce impurity, and the product that obtains does not need special purified and handles.
2, the present invention adopts the low molecular carboxylic acid salt and the long-chain carboxylic acid of metal ion to react with stoichiometric ratio, and removes low molecular carboxylic acid in reaction process, has improved the transformation efficiency and the controllability of metal ion.
3, the low molecular organic acids, water and the entrainer that produce of production process can not get polluting, can recycle, and environmental pollution has been avoided in no waste liquid discharge.
Claims (6)
1, a kind of preparation method of siccative is by the low molecular carboxylic acid salt M of metal ion
N+X
n -Or its aqueous solution and C
8-C
20Aliphatics or aromatic carboxylic acid directly in a reactor that has whipping appts, thermometer, a division box, react, generate (M
N+) (Y
-)
n, wherein M represents metal, and n is 1,2,3,4 or 5, and X is C
2-C
4Low molecular carboxylic acid, Y is aliphatics or the aromatic carboxylic acid of C8-C20, and the low molecular carboxylic acid that reaction produces is deviate from a kind of water and/or the separation of deviating from the reactive system as entrainer that it is characterized in that adding in reaction process in benzene, toluene, m-xylene, vinyl acetic monomer, N-BUTYL ACETATE, acetic acid lactone, chlorinated hydrocarbon or the ether compound.
2, the preparation method of siccative according to claim 1 is characterized in that said metal M is at least a among Co, Mn, Pb, Fe, Zn, Zr, Ce, Ni, Cu, Ca, the K.
3, the preparation method of siccative according to claim 1 and 2, it is characterized in that said entrainer can form azeotrope with water, and do not form azeotrope with carboxylic acid, perhaps in the azeotrope composition that entrainer and low molecular carboxylic acid form, low molecular carboxylic acid is occupied less mark, and maximum is no more than 50% weight percent content.
4, the preparation method of siccative according to claim 3 is characterized in that reacting the low molecular carboxylic acid of generation, the entrainer of recovery, and perhaps the azeotrope of entrainer and low molecular carboxylic acid and water can be used for recycling.
5, the preparation method of siccative according to claim 1, the outlet temperature that it is characterized in that reaction mass generally be lower than the long-chain carboxylic acid's boiling point of using more than 30 ℃.
6, the preparation method of siccative according to claim 1 or 5, the outlet temperature that it is characterized in that reaction mass be lower than the long-chain carboxylic acid's boiling point of using more than 50 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00110821A CN1116371C (en) | 2000-01-12 | 2000-01-12 | Method for preparing drier |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00110821A CN1116371C (en) | 2000-01-12 | 2000-01-12 | Method for preparing drier |
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| Publication Number | Publication Date |
|---|---|
| CN1261616A CN1261616A (en) | 2000-08-02 |
| CN1116371C true CN1116371C (en) | 2003-07-30 |
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|---|---|---|---|
| CN00110821A Expired - Fee Related CN1116371C (en) | 2000-01-12 | 2000-01-12 | Method for preparing drier |
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| CN116621690A (en) * | 2023-05-25 | 2023-08-22 | 沈阳张明化工有限公司 | A kind of preparation method of reagent grade aqueous drier zirconium isooctanoate |
| CN118427881B (en) * | 2024-06-25 | 2024-10-01 | 大连爱柏斯化工股份有限公司 | Cobalt propionate synthesis related data protection method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060668A (en) * | 1990-10-16 | 1992-04-29 | 福建省龙岩地区稀土科学研究所 | A kind of production method of rare-earth coatings drier |
-
2000
- 2000-01-12 CN CN00110821A patent/CN1116371C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060668A (en) * | 1990-10-16 | 1992-04-29 | 福建省龙岩地区稀土科学研究所 | A kind of production method of rare-earth coatings drier |
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