CN116969834B - Catalyst adipic acid recovery process method in beta-isophorone production process - Google Patents
Catalyst adipic acid recovery process method in beta-isophorone production process Download PDFInfo
- Publication number
- CN116969834B CN116969834B CN202311236042.0A CN202311236042A CN116969834B CN 116969834 B CN116969834 B CN 116969834B CN 202311236042 A CN202311236042 A CN 202311236042A CN 116969834 B CN116969834 B CN 116969834B
- Authority
- CN
- China
- Prior art keywords
- adipic acid
- beta
- isophorone
- rectifying tower
- controlled
- 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.)
- Active
Links
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 title claims abstract description 168
- LKOKKQDYMZUSCG-UHFFFAOYSA-N 3,5,5-Trimethyl-3-cyclohexen-1-one Chemical compound CC1=CC(C)(C)CC(=O)C1 LKOKKQDYMZUSCG-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 235000011037 adipic acid Nutrition 0.000 title claims abstract description 84
- 239000001361 adipic acid Substances 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000011084 recovery Methods 0.000 title claims abstract description 23
- 239000012528 membrane Substances 0.000 claims abstract description 47
- 238000004064 recycling Methods 0.000 claims abstract description 29
- 238000001471 micro-filtration Methods 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 21
- 239000000919 ceramic Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims description 33
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- -1 polydimethylsiloxane Polymers 0.000 claims description 11
- OBDSPDZCPRBIIA-UHFFFAOYSA-N 5-sulfanyl-3h-1,3-thiazole-2-thione Chemical compound SC1=CN=C(S)S1 OBDSPDZCPRBIIA-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- VPASWAQPISSKJP-UHFFFAOYSA-N ethyl prop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C=C VPASWAQPISSKJP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000011324 bead Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- 238000009835 boiling Methods 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000004069 differentiation Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000002262 Schiff base Substances 0.000 description 6
- 238000006317 isomerization reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- 244000000626 Daucus carota Species 0.000 description 1
- 235000002767 Daucus carota Nutrition 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
- B01D67/00931—Chemical modification by introduction of specific groups after membrane formation, e.g. by grafting
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Transplantation (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of catalysts and organic synthesis, and particularly relates to a catalyst adipic acid recovery process method in the beta-isophorone production process; the modified ceramic microfiltration membrane is adopted, wherein the organoboron and thiazole groups have the capability of coordinating with metal ion impurities in adipic acid, so that the organoboron and thiazole groups are adsorbed on the surface of the ceramic membrane, and the purity of the adipic acid is improved, so that the adipic acid can be recycled conveniently; according to the invention, a three-effect rectification method is adopted, adipic acid in beta-isophorone is separated according to boiling point differentiation of the beta-isophorone and adipic acid, and the method has the advantages of simple process, low equipment investment and the like; the invention can efficiently recycle the catalyst adipic acid in the beta-isophorone production process, has the advantages of cost reduction and efficiency enhancement, and improves the recycling rate of adipic acid.
Description
Technical Field
The invention relates to the field of catalysts and organic synthesis, in particular to a catalyst adipic acid recovery process method in the beta-isophorone production process.
Background
Beta-isophorone (3, 5-trimethyl-3-cyclohexen-1-one) is an isomer of alpha-isophorone and is a downstream fine chemical of acetone. Beta-isophorone has a mint-like flavor and can be used as a fragrance component. Beta-isophorone is an important raw material for synthesizing fine chemicals such as carrots, medicines and the like, and is particularly used as a raw material for efficiently preparing isophorone (2, 6-trimethyl-2-cyclohexene-1, 4-dione) which is one of main components of tobacco flavors.
Chinese patent CN115433067a: a method for preparing beta-isophorone is provided. The alpha-isophorone added with the auxiliary agent is subjected to isomerization reaction in a tubular reactor in a pressurizing high-temperature mode, the reaction liquid is subjected to reduced pressure rectification to obtain a beta-isophorone product, the product content is more than 99.5%, an alkaline catalyst is not used in the reaction, the residence time of the reaction liquid at high temperature is shortened through the use of the auxiliary agent and the optimization of the reactor, the product stability is improved, the generation of heavy components is avoided, the yield of the beta-isophorone product is more than 99%, and the industrial production is facilitated.
Chinese patent CN111215138B: an N- (2-hydroxyethyl) diethylenetriamine Schiff base catalyst, a preparation method and application thereof in preparing beta-isophorone are provided. The preparation method of the catalyst comprises the following steps: 1) Preparing bis-Schiff base by reacting diethylenetriamine with aromatic aldehyde; 2) The bis-Schiff base compound reacts with ethylene oxide to obtain the N- (2-hydroxyethyl) diethylenetriamine Schiff base. The invention also provides a method for preparing and generating beta-isophorone by isomerization reaction of alpha-isophorone under the action of the Schiff base. The catalyst of the method is simple to prepare and easy to industrialize. The prepared N- (2-hydroxyethyl) diethylenetriamine Schiff base has high selectivity and high yield for the reaction of isomerizing alpha-isophorone to beta-isophorone, byproducts are not easy to generate, and the catalyst is easy for industrial production and has no corrosion to equipment.
Chinese patent CN112517075B: an isomerization catalyst, its preparing process and the preparing process of beta-isophorone are disclosed. The structural formula of the isomerization catalyst is shown as follows: m represents Cr, mn, fe, co, ni, cu, zn. The catalyst has high selectivity and high yield for the reaction of isomerizing alpha-isophorone to beta-isophorone, the preparation of the catalyst is simple, active groups are loaded on a carrier through chemical bonds, the stability of the catalyst is strong, and the catalyst can be reused without obvious activity loss. The catalyst and benzoquinone and naphthoquinone substances are used as auxiliary agents, and the alpha-isophorone is subjected to isomerization reaction to prepare beta-isophorone, so that the selectivity is high, and Michael addition and carbonyl condensation side reactions can be inhibited.
The catalyst for preparing beta-isophorone mainly comprises high-boiling solid acid, acetylacetone compound of transition metal, alkali metal compound, acidic ceramic, molecular sieve and the like, and although the catalytic efficiency of adipic acid is lower than that of other catalysts, the catalyst is low in price, has better solubility and stability under the reaction condition, and is not easy to cause coking and turbidity. Therefore, how to efficiently recycle the catalyst adipic acid in the beta-isophorone production process so as to bring the catalyst adipic acid into play with the maximum catalytic performance is the aim of the research of the invention.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a catalyst adipic acid recovery process method in the beta-isophorone production process, which adopts a modified ceramic microfiltration membrane to improve the purity of adipic acid so as to facilitate recycling, adopts a three-effect rectification method to separate adipic acid in beta-isophorone, and has the advantages of simple process, less equipment investment and the like.
The specific technical scheme of the invention is as follows:
a catalyst adipic acid recovery process method in the beta-isophorone production process comprises the following operation steps:
s1: the reacted beta-isophorone mixed solution is sent to a first rectifying tower, the tower top distillate enters a second rectifying tower, and the tower bottom liquid is recycled to an adipic acid recycling tank;
s2: the distillate at the top of the second rectifying tower enters a third rectifying tower, and the tower bottom liquid is recycled to the adipic acid recycling tank;
s3: the distillate at the top of the third rectifying tower enters a beta-isophorone tank, and the tower bottom liquid is recycled to an adipic acid recycling tank;
s4: adipic acid in the adipic acid recovery tank is pumped to a reaction kettle after being separated by a membrane separator, and is used for continuously producing beta-isophorone and recycling.
In the technical scheme, the mass ratio of adipic acid to isophorone in the reacted beta-isophorone mixed solution is 1:3-15.
In the technical scheme, the rectifying tower is a thorn-shaped rectifying column or a glass bead packed column or a stainless steel theta ring packed column.
In the technical scheme, the temperature of the top of the first rectifying tower is controlled to be 120-160 ℃, and the temperature of the tower bottom is controlled to be 250-280 ℃.
In the technical scheme, the temperature of the top of the second rectifying tower is controlled to be 140-180 ℃, and the temperature of the tower bottom is controlled to be 260-300 ℃.
In the technical scheme, the temperature of the top of the third rectifying tower is controlled to be 120-140 ℃, and the temperature of the tower bottom is controlled to be 250-280 ℃.
In the technical scheme, the reflux ratio of the first rectifying tower is controlled to be 15-20.
In the technical scheme, the reflux ratio of the second rectifying tower is controlled to be 8-12.
In the technical scheme, the reflux ratio of the third rectifying tower is controlled to be 8-12.
In the technical scheme, the membrane separator adopts a modified ceramic microfiltration membrane, and the preparation method comprises the following steps:
s1: putting the mixture into a reaction kettle according to parts by weight, adding 10-17 parts of dihydroxy polydimethylsiloxane, dissolving the mixture into 1000-2000 parts of ethanol, adding 50-100 parts of dried tubular alumina ceramic microfiltration membrane with the average pore diameter of 100-300nm, and soaking and modifying the tubular alumina ceramic microfiltration membrane for 30-100 minutes at the temperature of 30-50 ℃;
s2: adding 5-10 parts of isocyanate ethyl acrylate and 0.05-0.5 part of dibutyl tin dilaurate, heating to 60-70 ℃ for reaction for 120-180 minutes,
s3: then adding 10-18 parts of 2, 5-dimercaptothiazole and 2-5 parts of triethylamine, heating to 60-70 ℃ for reaction for 60-100 minutes, adding 0.01-0.4 part of tripropenyl boron, reacting for 30-80 minutes, taking out the membrane tube, washing with water, and drying to obtain the modified ceramic microfiltration membrane.
Reaction mechanism:
1. the dihydroxy polydimethylsiloxane reacts with the surface hydroxyl groups of the tubular alumina ceramic microfiltration membrane to obtain the dihydroxy modified tubular alumina ceramic microfiltration membrane;
2. isocyanate ethyl acrylate reacts with a dihydroxy modified tubular alumina ceramic microfiltration membrane, the obtained acrylic acid group and 2, 5-dimercaptothiazole perform a mercapto-alkene addition reaction, and simultaneously, tripropenyl boron and 2, 5-dimercaptothiazole perform a mercapto-alkene addition reaction, so that the tubular alumina ceramic microfiltration membrane with the surface grafted with organic boron and thiazole is obtained.
The technical effects are as follows:
compared with the prior art, the catalyst adipic acid recovery process method in the beta-isophorone production process has the following remarkable effects:
1. because adipic acid is easy to complex with metal impurities in a reaction kettle, the metal impurities are easy to bring into a production system of beta-isophorone, the purity of the beta-isophorone is further influenced, and organoboron and thiazole groups have the capability of coordinating with metal ion impurities in the adipic acid; in this case, the adsorption can be achieved by formation of coordination bonds, i.e., metal ions form coordination bonds with a plurality of organoboron or thiazole groups, so as to be adsorbed on the surface of the ceramic membrane, thereby improving the purity of adipic acid for recycling;
2. according to the invention, a three-effect rectification method is adopted, adipic acid in beta-isophorone is separated according to boiling point differentiation of the beta-isophorone and adipic acid, and the method has the advantages of simple process, low equipment investment and the like;
3. the invention can efficiently recycle the catalyst adipic acid in the beta-isophorone production process, has the advantages of cost reduction and efficiency enhancement, and improves the recycling rate of adipic acid.
Drawings
FIG. 1 is a graph of the carbon 13 nuclear magnetic resonance spectrum of the beta-isophorone product prepared by catalysis with adipic acid purified in example 3.
Detailed Description
The technical scheme of the invention is further described by the following specific examples, but the specific details of the examples are only for illustrating the invention and do not represent all technical methods under the concept of the invention. And therefore should not be construed as limiting the overall scope of the invention.
Example 1
A catalyst adipic acid recovery process method in the beta-isophorone production process comprises the following operation steps:
s1: the reacted beta-isophorone mixed solution is sent to a first rectifying tower, the tower top distillate enters a second rectifying tower, and the tower bottom liquid is recycled to an adipic acid recycling tank;
s2: the distillate at the top of the second rectifying tower enters a third rectifying tower, and the tower bottom liquid is recycled to the adipic acid recycling tank;
s3: the distillate at the top of the third rectifying tower enters a beta-isophorone tank, and the tower bottom liquid is recycled to an adipic acid recycling tank;
s4: adipic acid in the adipic acid recovery tank is pumped to a reaction kettle after being separated by a membrane separator, and is used for continuously producing beta-isophorone and recycling.
The mass ratio of adipic acid to isophorone in the reacted beta-isophorone mixed solution is 1:3.
The rectifying tower is a thorn-shaped rectifying column.
The temperature of the top of the first rectifying tower is controlled at 120 ℃, and the temperature of the tower bottom is controlled at 250 ℃.
The temperature of the top of the second rectifying tower is controlled at 140 ℃, and the temperature of the bottom of the second rectifying tower is controlled at 260 ℃.
The temperature of the top of the third rectifying tower is controlled at 120 ℃, and the temperature of the bottom of the third rectifying tower is controlled at 250 ℃.
The reflux ratio of the first rectifying tower is controlled at 15.
And the reflux ratio of the second rectifying tower is controlled at 8.
And the reflux ratio of the third rectifying tower is controlled at 8.
The membrane separator adopts a modified ceramic microfiltration membrane, and the preparation method comprises the following steps:
s1: putting into a reaction kettle, adding 10kg of dihydroxy polydimethylsiloxane, dissolving in 1000kg of ethanol, adding 50kg of dried tubular alumina ceramic microfiltration membrane with average pore diameter of 100nm, and soaking and modifying for 30 minutes at 30 ℃;
s2: then adding 5kg of isocyanate ethyl acrylate and 0.05kg of dibutyl tin dilaurate, heating to 60 ℃ for reaction for 120 minutes,
s3: then 10kg of 2, 5-dimercaptothiazole and 2kg of triethylamine are added, the temperature is raised to 60 ℃ for reaction for 60 minutes, then 0.01kg of tripropenyl boron is added for reaction for 30 minutes, the membrane tube is taken out, washed and dried, and the modified ceramic microfiltration membrane is obtained.
Example 2
A catalyst adipic acid recovery process method in the beta-isophorone production process comprises the following operation steps:
s1: the reacted beta-isophorone mixed solution is sent to a first rectifying tower, the tower top distillate enters a second rectifying tower, and the tower bottom liquid is recycled to an adipic acid recycling tank;
s2: the distillate at the top of the second rectifying tower enters a third rectifying tower, and the tower bottom liquid is recycled to the adipic acid recycling tank;
s3: the distillate at the top of the third rectifying tower enters a beta-isophorone tank, and the tower bottom liquid is recycled to an adipic acid recycling tank;
s4: adipic acid in the adipic acid recovery tank is pumped to a reaction kettle after being separated by a membrane separator, and is used for continuously producing beta-isophorone and recycling.
The mass ratio of adipic acid to isophorone in the reacted beta-isophorone mixed solution is 1:8.
The rectifying tower is a glass bead filling column.
The temperature of the top of the first rectifying tower is controlled at 130 ℃, and the temperature of the bottom of the first rectifying tower is controlled at 260 ℃.
The temperature of the top of the second rectifying tower is controlled at 150 ℃, and the temperature of the bottom of the second rectifying tower is controlled at 270 ℃.
The temperature of the top of the third rectifying tower is controlled at 125 ℃, and the temperature of the bottom of the third rectifying tower is controlled at 260 ℃.
The reflux ratio of the first rectifying tower is controlled at 16.
The reflux ratio of the second rectifying tower is controlled at 9.
And the reflux ratio of the third rectifying tower is controlled at 9.
The membrane separator adopts a modified ceramic microfiltration membrane, and the preparation method comprises the following steps:
s1: putting into a reaction kettle, adding 12kg of dihydroxy polydimethylsiloxane, dissolving in 1350kg of ethanol, adding 70kg of dried tubular alumina ceramic microfiltration membrane with average pore diameter of 200nm, and soaking and modifying at 35 ℃ for 60 minutes;
s2: then adding 6kg of isocyanate ethyl acrylate and 0.2kg of dibutyl tin dilaurate, heating to 65 ℃ for reaction for 140 minutes,
s3: then adding 12kg of 2, 5-dimercaptothiazole, 3kg of triethylamine, heating to 65 ℃ for reaction for 70 minutes, adding 0.2kg of tripropenyl boron, reacting for 50 minutes, taking out a membrane tube, washing with water, and drying to obtain the modified ceramic microfiltration membrane.
Example 3
A catalyst adipic acid recovery process method in the beta-isophorone production process comprises the following operation steps:
s1: the reacted beta-isophorone mixed solution is sent to a first rectifying tower, the tower top distillate enters a second rectifying tower, and the tower bottom liquid is recycled to an adipic acid recycling tank;
s2: the distillate at the top of the second rectifying tower enters a third rectifying tower, and the tower bottom liquid is recycled to the adipic acid recycling tank;
s3: the distillate at the top of the third rectifying tower enters a beta-isophorone tank, and the tower bottom liquid is recycled to an adipic acid recycling tank;
s4: adipic acid in the adipic acid recovery tank is pumped to a reaction kettle after being separated by a membrane separator, and is used for continuously producing beta-isophorone and recycling.
The mass ratio of adipic acid to isophorone in the reacted beta-isophorone mixed solution is 1:13.
The rectifying tower is a glass bead filling column.
The temperature of the top of the first rectifying tower is controlled at 150 ℃, and the temperature of the bottom of the first rectifying tower is controlled at 270 ℃.
The temperature of the top of the second rectifying tower is controlled at 170 ℃, and the temperature of the bottom of the second rectifying tower is controlled at 290 ℃.
The temperature of the top of the third rectifying tower is controlled at 135 ℃ and the temperature of the bottom of the third rectifying tower is controlled at 270 ℃.
The reflux ratio of the first rectifying tower is controlled at 18.
The reflux ratio of the second rectifying tower is controlled at 11.
And the reflux ratio of the third rectifying tower is controlled at 11.
The membrane separator adopts a modified ceramic microfiltration membrane, and the preparation method comprises the following steps:
s1: putting into a reaction kettle, adding 16kg of dihydroxy polydimethylsiloxane, dissolving in 1800kg of ethanol, adding 90kg of dried tubular alumina ceramic microfiltration membrane with average pore diameter of 200nm, and soaking and modifying for 90 minutes at 45 ℃;
s2: then 8kg of isocyanate ethyl acrylate and 0.4kg of dibutyl tin dilaurate are added, the temperature is raised to 65 ℃ for reaction for 160 minutes,
s3: then 16kg of 2, 5-dimercaptothiazole, 4kg of triethylamine are added, the temperature is raised to 65 ℃ for reaction for 90 minutes, then 0.3kg of tripropenyl boron is added for reaction for 70 minutes, the membrane tube is taken out, washed and dried, and the modified ceramic microfiltration membrane is obtained.
Example 4
A catalyst adipic acid recovery process method in the beta-isophorone production process comprises the following operation steps:
s1: the reacted beta-isophorone mixed solution is sent to a first rectifying tower, the tower top distillate enters a second rectifying tower, and the tower bottom liquid is recycled to an adipic acid recycling tank;
s2: the distillate at the top of the second rectifying tower enters a third rectifying tower, and the tower bottom liquid is recycled to the adipic acid recycling tank;
s3: the distillate at the top of the third rectifying tower enters a beta-isophorone tank, and the tower bottom liquid is recycled to an adipic acid recycling tank;
s4: adipic acid in the adipic acid recovery tank is pumped to a reaction kettle after being separated by a membrane separator, and is used for continuously producing beta-isophorone and recycling.
The mass ratio of adipic acid to isophorone in the reacted beta-isophorone mixed solution is 1:15.
The rectifying tower is a stainless steel theta ring filling column.
The temperature of the top of the first rectifying tower is controlled at 160 ℃, and the temperature of the bottom of the first rectifying tower is controlled at 280 ℃.
The temperature of the top of the second rectifying tower is controlled at 180 ℃, and the temperature of the bottom of the second rectifying tower is controlled at 300 ℃.
The temperature of the top of the third rectifying tower is controlled at 140 ℃, and the temperature of the bottom of the third rectifying tower is controlled at 280 ℃.
The reflux ratio of the first rectifying tower is controlled at 20.
The reflux ratio of the second rectifying tower is controlled at 12.
And the reflux ratio of the third rectifying tower is controlled at 12.
The membrane separator adopts a modified ceramic microfiltration membrane, and the preparation method comprises the following steps:
s1: putting into a reaction kettle, adding 17kg of dihydroxy polydimethylsiloxane, dissolving in 2000kg of ethanol, adding 100kg of dried tubular alumina ceramic microfiltration membrane with average pore diameter of 300nm, and soaking and modifying for 100 minutes at 50 ℃;
s2: then 10kg of isocyanate ethyl acrylate and 0.5kg of dibutyl tin dilaurate are added, the temperature is raised to 70 ℃ for reaction for 180 minutes,
s3: then 18kg of 2, 5-dimercaptothiazole, 5kg of triethylamine are added, the temperature is raised to 70 ℃ for reaction for 100 minutes, then 0.4kg of tripropenyl boron is added for reaction for 80 minutes, the membrane tube is taken out, washed and dried, and the modified ceramic microfiltration membrane is obtained.
Comparative example 1
The procedure of example 1 was repeated except that no dihydroxypolydimethylsiloxane was added.
Comparative example 2
The procedure of example 1 was repeated except that ethyl acrylate isocyanate was not added.
Comparative example 3
2, 5-dimercaptothiazole was not added, and the procedure of example 1 was followed.
The recovery of adipic acid in the above embodiments is calculated according to the following formula:
recovery of adipic acid = adipic acid content in adipic acid recovery tank/adipic acid content of beta-isophorone mixture after reaction x 100%
Through the data analysis of the above examples and comparative examples, the modified ceramic microfiltration membrane adopted by the invention can effectively improve the purity of adipic acid so as to be convenient for recycling; the catalyst adipic acid recovery process method in the beta-isophorone production process has the advantages of cost reduction, synergy and capability of effectively improving the adipic acid recovery utilization rate.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and those skilled in the art may modify or substitute the technical solution of the present invention, and the scope of the present invention is defined by the claims.
Claims (9)
1. A catalyst adipic acid recovery process method in the beta-isophorone production process comprises the following operation steps:
s1: the reacted beta-isophorone mixed solution is sent to a first rectifying tower, the tower top distillate enters a second rectifying tower, and the tower bottom liquid is recycled to an adipic acid recycling tank;
s2: the distillate at the top of the second rectifying tower enters a third rectifying tower, and the tower bottom liquid is recycled to the adipic acid recycling tank;
s3: the distillate at the top of the third rectifying tower enters a beta-isophorone tank, and the tower bottom liquid is recycled to an adipic acid recycling tank;
s4: adipic acid in the adipic acid recovery tank is pumped to a reaction kettle after being separated by a membrane separator, and is used for continuously producing beta-isophorone and recycling;
the membrane separator adopts a modified ceramic microfiltration membrane, and the preparation method comprises the following steps:
s1: putting the mixture into a reaction kettle according to parts by weight, adding 10-17 parts of dihydroxy polydimethylsiloxane, dissolving the mixture into 1000-2000 parts of ethanol, adding 50-100 parts of dried tubular alumina ceramic microfiltration membrane with the average pore diameter of 100-300nm, and soaking and modifying the tubular alumina ceramic microfiltration membrane for 30-100 minutes at the temperature of 30-50 ℃;
s2: adding 5-10 parts of isocyanate ethyl acrylate and 0.05-0.5 part of dibutyltin dilaurate, heating to 60-70 ℃ and reacting for 120-180 minutes;
s3: then adding 10-18 parts of 2, 5-dimercaptothiazole and 2-5 parts of triethylamine, heating to 60-70 ℃ for reaction for 60-100 minutes, adding 0.01-0.4 part of tripropenyl boron, reacting for 30-80 minutes, taking out the membrane tube, washing with water, and drying to obtain the modified ceramic microfiltration membrane.
2. The process for recovering adipic acid catalyst in the production process of beta-isophorone according to claim 1, wherein the process comprises the following steps: the mass ratio of adipic acid to isophorone in the reacted beta-isophorone mixed solution is 1:3-15.
3. The process for recovering adipic acid catalyst in the production process of beta-isophorone according to claim 1, wherein the process comprises the following steps: the rectifying tower is a thorn rectifying column or a glass bead packed column or a stainless steel theta ring packed column.
4. The process for recovering adipic acid catalyst in the production process of beta-isophorone according to claim 1, wherein the process comprises the following steps: the temperature of the top of the first rectifying tower is controlled to be 120-160 ℃, and the temperature of the tower bottom is controlled to be 250-280 ℃.
5. The process for recovering adipic acid catalyst in the production process of beta-isophorone according to claim 1, wherein the process comprises the following steps: the temperature of the top of the second rectifying tower is controlled between 140 and 180 ℃, and the temperature of the bottom of the second rectifying tower is controlled between 260 and 300 ℃.
6. The process for recovering adipic acid catalyst in the production process of beta-isophorone according to claim 1, wherein the process comprises the following steps: the temperature of the top of the third rectifying tower is controlled to be 120-140 ℃, and the temperature of the tower bottom is controlled to be 250-280 ℃.
7. The process for recovering adipic acid catalyst in the production process of beta-isophorone according to claim 1, wherein the process comprises the following steps: the reflux ratio of the first rectifying tower is controlled to be 15-20.
8. The process for recovering adipic acid catalyst in the production process of beta-isophorone according to claim 1, wherein the process comprises the following steps: the reflux ratio of the second rectifying tower is controlled to be 8-12.
9. The process for recovering adipic acid catalyst in the production process of beta-isophorone according to claim 1, wherein the process comprises the following steps: the reflux ratio of the third rectifying tower is controlled to be 8-12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311236042.0A CN116969834B (en) | 2023-09-25 | 2023-09-25 | Catalyst adipic acid recovery process method in beta-isophorone production process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311236042.0A CN116969834B (en) | 2023-09-25 | 2023-09-25 | Catalyst adipic acid recovery process method in beta-isophorone production process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116969834A CN116969834A (en) | 2023-10-31 |
| CN116969834B true CN116969834B (en) | 2023-12-08 |
Family
ID=88471669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311236042.0A Active CN116969834B (en) | 2023-09-25 | 2023-09-25 | Catalyst adipic acid recovery process method in beta-isophorone production process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116969834B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112920032A (en) * | 2019-12-06 | 2021-06-08 | 万华化学集团股份有限公司 | Preparation method of beta-isophorone |
-
2023
- 2023-09-25 CN CN202311236042.0A patent/CN116969834B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112920032A (en) * | 2019-12-06 | 2021-06-08 | 万华化学集团股份有限公司 | Preparation method of beta-isophorone |
Non-Patent Citations (5)
| Title |
|---|
| C_4~C_6混合二元酸的分离;段练;朱建华;王瑞;;山东化工(10);全文 * |
| α-异佛尔酮异构制备β-异佛尔酮的研究;龙姝;曹忠;李传生;吕品;骆跃;黄茜茜;;食品与机械(01);全文 * |
| 从环己烷氧化液酸洗水中回收己二酸的技术进展;樊丽华;马沛生;杨长生;相政乐;;精细石油化工(02);全文 * |
| 异佛尔酮及氧化异佛尔酮合成工艺的研究进展;叶启亮, 周文勇, 孙浩, 房鼎业;化工进展(10);全文 * |
| 异佛尔酮合成技术进展与应用开发;吕咏梅;化学推进剂与高分子材料(04);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116969834A (en) | 2023-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109456200B (en) | Preparation method of m-xylylenediamine | |
| CN101475473A (en) | Method for preparing oxalate by coupling reaction of CO | |
| CN115433067B (en) | Preparation method of beta-isophorone | |
| CN102219680B (en) | Method for preparing oxalic ester by CO gas-phase process | |
| CN111215138B (en) | Catalyst, preparation method and application of catalyst in preparation of beta-isophorone | |
| CN110563554B (en) | Method for producing adiponitrile | |
| CN116969834B (en) | Catalyst adipic acid recovery process method in beta-isophorone production process | |
| CN111574378B (en) | Method for efficiently synthesizing dihydroxy ethyl terephthalate without catalysis | |
| CN114380698B (en) | Method for synthesizing methylcyclohexanediamine by selective hydrogenation of diaminotoluene by continuous method | |
| CN110903181B (en) | Method for preparing p-benzoquinone compound by double-catalytic system | |
| CN101993363B (en) | Method for preparing oxalic ester by CO coupling | |
| CN113072461B (en) | Preparation method of butanone oxime | |
| CN101993365A (en) | Method for producing oxalic ester by CO coupling | |
| CN101993364A (en) | Method for producing oxalic ester by gas phase CO coupling | |
| CN112279783B (en) | Method for preparing 3-hydroxypropionitrile under supercritical condition | |
| CN115806534B (en) | Preparation method of 5-hydroxymethylfurfural | |
| CN112661619B (en) | Method for preparing cyclopentanone | |
| CN115819185B (en) | Method for synthesizing neopentyl glycol | |
| CN102219676B (en) | Method for preparing oxalate by CO coupling | |
| CN115850116B (en) | Solvent-free supercritical catalytic synthesis method of 1, 5-pentanediisocyanate | |
| CN117417262B (en) | Preparation method of diglycolamine | |
| CN117756650A (en) | Preparation method of monoisopropanolamine | |
| CN114276216A (en) | Method for removing aldehyde impurities in 1, 3-propylene glycol | |
| CN117776926A (en) | Recycling method for residue of rectifying still | |
| CN117486842A (en) | Method and device for producing succinic anhydride by maleic anhydride gas-phase hydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |