CN105778771A - Method for directly preparing disproportionated rosin from rosin through taking iodine as catalyst - Google Patents
Method for directly preparing disproportionated rosin from rosin through taking iodine as catalyst Download PDFInfo
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- CN105778771A CN105778771A CN201610267032.7A CN201610267032A CN105778771A CN 105778771 A CN105778771 A CN 105778771A CN 201610267032 A CN201610267032 A CN 201610267032A CN 105778771 A CN105778771 A CN 105778771A
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- China
- Prior art keywords
- rosin
- catalyst
- disproportionated rosin
- iodine
- colophonium
- Prior art date
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 48
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 47
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052740 iodine Inorganic materials 0.000 title claims abstract description 19
- 239000011630 iodine Substances 0.000 title claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000004090 dissolution Methods 0.000 claims abstract description 5
- 238000004062 sedimentation Methods 0.000 claims abstract description 5
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000007323 disproportionation reaction Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 230000006835 compression Effects 0.000 claims description 6
- 238000007906 compression Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000005352 clarification Methods 0.000 claims description 4
- 238000004299 exfoliation Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 2
- 229910052756 noble gas Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract 4
- 238000004321 preservation Methods 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 4
- 235000011613 Pinus brutia Nutrition 0.000 description 4
- 241000018646 Pinus brutia Species 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 description 2
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Natural products OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical compound OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 description 2
- 229940118781 dehydroabietic acid Drugs 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention discloses a method for directly preparing disproportionated rosin from rosin through taking iodine as a catalyst. The method comprises the following steps: 1) conveying the rosin from a sedimentation tank to a dissolver for dissolution and enabling dissolved rosin liquid to enter a clarifying tank; 2) introducing protective gas, leaving the dissolved rosin liquid to stand in the clarifying tank, automatically layering the rosin liquid with water and conveying clarified clean rosin liquid to a reactor; 3) under the environment of the protective gas, raising the temperature of the reactor to 250-270 DEG C and performing heat preservation for 30-60 minutes; 4) maintaining the environment of the protective gas, reducing the temperature to below 160 DEG C and adding the iodine ceramsite catalyst; 5) maintaining the environment of the protective gas, raising the temperature to 280-290 DEG C and performing heat preservation for 120-240 minutes; 6) reducing the temperature, filtering so as to remove the catalyst mixed in a reaction product when the product is in a liquid state to prepare the disproportionated rosin. According to the preparation method of the disproportionated rosin, disclosed by the invention, the consumption of the late catalyst is reduced, the production cost is reduced, and the disproportionated rosin is higher in acid value, lighter in color and higher in yield.
Description
Technical field
The invention belongs to Colophonium field of deep, particularly relate to a kind of directly be prepared disproportionation pine with iodine by Colophonium for catalyst
Fragrant method.
Background technology
The main component of Colophonium is for being C by molecular formula20H30O2Resinic acid composition compound, such resinic acid is for having
Unitary shuttle containing two double bonds acid of three ring phenanthrene skeletons, the double bond of Colophonium is conjugated double bond, and chemism is strong, thus generally needs
To be hydrogenated with it, dismutation reaction etc. processes to generate the Colophonium of stabilisation.Wherein, relative to hydrogenated rosin, disproportionated rosin
Relatively low due to production cost thus amount ratio of market is bigger.Disproportionated rosin mainly produces in the emulsion such as synthetic rubber, ABS resin
In be used as emulsifying agent, be also to manufacture rosin spirit and the raw material of rosin amine, be also largely used to manufacture water-soluble pressure-sensitive adhesive, printing
Its main component dehydroabietic acid of ink, organic pigment etc., particularly discovered in recent years can be as producing the former of physiologically active material
Material, and also there is optical activity, therefore, disproportionated rosin has potential extensive application valency in medicine, pesticide, chemistry, optics
Value.
In terms of preparing disproportionated rosin, most work is around the research expansion of two aspects: the first is to urging
The selection of agent, this respect research is the most, therefore have also been developed some rosin-disproportionatings just having good catalytic effect anti-
Answer catalyst;On the other hand being the research of preparation technology, this respect research is less, and the most topmost existing technique is Colophonium
Body adds catalyst be heated to assigned temperature, carry out the reaction of corresponding time and be prepared from;Also have is exactly that Colophonium is dissolved in
Solvent adds catalyst be heated to assigned temperature, carry out the reaction of corresponding time and be prepared from.Current commercial produces disproportionation
Colophonium mainly Colophonium body adds catalyst be heated to assigned temperature, carry out the reaction of corresponding time and be prepared from.How
Reducing the consumption of catalyst, reducing cost is current subject matter.
Summary of the invention
The goal of the invention of the present invention is to provide a kind of method directly being prepared disproportionated rosin with iodine for catalyst by Colophonium.
For solving above-mentioned technical problem, the technical solution used in the present invention is:
The method directly being prepared disproportionated rosin with iodine for catalyst by Colophonium, the method includes:
1) Colophonium is put into Sedimentation tank, with conveying worm, Colophonium is delivered to dissolvers and dissolve, during dissolving, add Oleum Terebinthinae and water,
Leading to into steam during dissolving, temperature controls at 90-95 DEG C；The fat liquid dissolved defecator in dissolvers removes thick impurity
Rear entrance defecator;
2) being passed through protection gas, the fat liquid of dissolving stands 6-8 hour in defecator, makes fat liquid and water self exfoliation, after clarification
Clean fat liquid processed is sent to reactor directly as the raw material of dismutation reaction;
3) in the environment of protection gas, reactor is warmed up to 250-270 DEG C, is incubated 30-60 minute;
4) maintaining protection compression ring border, temperature of reactor is down to less than 160 DEG C, be slowly added into iodine ceramsite catalyst, described iodine is made pottery
Prepare in iodine catalyst is attached to porous ceramic grain surface and micropore by grain catalyst;
5) maintain protection compression ring border, be warmed up to 280 DEG C-290 DEG C, be incubated 120-240 minute;
6) reduce temperature, and be filtered to remove the catalyst being mixed with in product when product is in liquid, i.e. prepare disproportionation pine
Fragrant.
The above-mentioned method preparing disproportionated rosin, wherein, the gross mass of described Oleum Terebinthinae and water be Colophonium quality 0.5～
0.7 times;Described Oleum Terebinthinae is 1:1～1:3 with the mass volume ratio of water.
The above-mentioned method preparing disproportionated rosin, wherein, the Oleum Terebinthinae being evaporated in described Colophonium course of dissolution and water
Steam is reclaimed by the condenser of dissolvers.
The above-mentioned method preparing disproportionated rosin, wherein, water and the terebinthine steam of the effusion of described defecator enter cold
Condenser reclaims, and the slag-water slurry of bottom is discharged by stable can.
The above-mentioned method preparing disproportionated rosin, wherein, the described a diameter of 0.1-1mm of iodine ceramsite catalyst.
The above-mentioned method preparing disproportionated rosin, wherein, described protection gas is noble gas or nitrogen.
The above-mentioned method preparing disproportionated rosin, wherein, step 3) in, mixing speed is 300～500 turns/min.
The above-mentioned method preparing disproportionated rosin, wherein, described step 6) in, temperature is reduced to 200～250 DEG C.
In sum, owing to have employed technique scheme, the invention has the beneficial effects as follows:
1) method preparing disproportionated rosin of the present invention, uses first Colophonium high-temperature process, makes Colophonium at high temperature be disproportionated
Reaction, after allowing part abietic acid change into dehydroabietic acid, then carries out subsequent treatment so that in late phase reaction, the consumption of catalyst is notable
Reduce, be effectively reduced production cost;
2) method preparing disproportionated rosin of the present invention, uses iodine ceramsite catalyst, and specific surface area is big, makes catalytic efficiency higher；
Haydite easily filters removal relatively greatly, thus improves the quality of product;
3) disproportionated rosin that the method preparing disproportionated rosin of the present invention prepares, acid number is higher, color is more shallow, and productivity is higher；
4) method preparing disproportionated rosin of the present invention, with Colophonium directly as dismutation reaction raw material, eliminates and is made up of fat liquid
The process of Colophonium, thus simplify flow process, investment reduction also reduces cost, it is thus also avoided that heating and melting makes product colour become repeatedly
Deep problem.
Accompanying drawing explanation
Fig. 1 is the present invention；The process chart of disproportionated rosin process of preparing
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is further described.
Embodiment 1
1) 2 tons of Colophonium are put into Sedimentation tank, with conveying worm, Colophonium is delivered to dissolvers and dissolve, during dissolving, add 600kg pine
Fuel-economizing and 600kg water, lead to into steam during dissolving, temperature controls at about 90 DEG C, the Oleum Terebinthinae being evaporated in course of dissolution and
Steam is reclaimed by the condenser on dissolvers top；The fat liquid dissolved is after the defecator in dissolvers removes thick impurity
Enter defecator;
2) being passed through protection gas, the fat liquid of dissolving stands 6 hours in defecator, makes fat liquid and water self exfoliation, clean after clarification
Fat liquid processed is sent to reactor directly as the raw material of dismutation reaction;Water and the terebinthine steam of defecator effusion enter condenser
Reclaim, the slag-water slurry of bottom, discharged by stable can.The intermediate layer that moisture, fine impurities and a small amount of dark-coloured Colophonium are formed
It is sent into middle-layer resin liquid defecator, reclaims fat liquid therein；
3) in the environment of protection gas, reactor is warmed up to 250 DEG C, and mixing speed is 300 turns/min, is incubated 30 minutes;
4) maintain protection compression ring border, cool the temperature to 160 DEG C, be slowly added into iodine ceramsite catalyst;
5) maintain protection compression ring border, be warmed up to 280 DEG C, be incubated 120 minutes;
6) when temperature is reduced to 200 DEG C, product is put in filter, and be filtered to remove reaction when product is in liquid
The catalyst being mixed with in product, i.e. prepares disproportionated rosin.
Embodiment 2
1) 4 tons of Colophonium are put into Sedimentation tank, with conveying worm, Colophonium is delivered to dissolvers and dissolve, during dissolving, add 1200kg pine
Fuel-economizing and 1200kg water, lead to into steam during dissolving, temperature controls at about 95 DEG C, the Oleum Terebinthinae being evaporated in course of dissolution and
Steam is reclaimed by the condenser on dissolvers top；The fat liquid dissolved is after the defecator in dissolvers removes thick impurity
Enter defecator;
2) being passed through nitrogen, the fat liquid of dissolving stands 8 hours in defecator, makes fat liquid and water self exfoliation, the clean system after clarification
Fat liquid is sent to reactor directly as the raw material of dismutation reaction;The water of defecator effusion and terebinthine steam enter condenser and return
Receive, the slag-water slurry of bottom, discharged by stable can.The intermediate layer that moisture, fine impurities and a small amount of dark-coloured Colophonium are formed is sent
Enter middle-layer resin liquid defecator, reclaim fat liquid therein；
3) in the environment of nitrogen, reactor is warmed up to 270 DEG C, and mixing speed is 500 turns/min, is incubated 60 minutes;
4) maintain nitrogen environment, cool the temperature to 150 DEG C, be slowly added into iodine ceramsite catalyst;
5) maintain nitrogen environment, be warmed up to 290 DEG C, be incubated 240 minutes;
6) when temperature is reduced to 250 DEG C, product is put in filter, and be filtered to remove reaction when product is in liquid
The catalyst being mixed with in product, i.e. prepares disproportionated rosin.
Table 1: disproportionated rosin quality and national standard comparison obtained by this law are as follows:
| Project | National standard (one-level) | Embodiment 1 | Embodiment 2 |
| Color | Micro-Huang | Micro-Huang | Micro-Huang |
| Outward appearance | Transparent | Transparent | Transparent |
| Softening point (ring and ball method)/DEG C, >= | 76 | 76 | 76 |
| Acid value a/(mg/g), >= | 160 | 160 | 166 |
| Unsaponifiable matter content b/ (%) ,≤ | 5 | 4 | 5 |
| Alcohol-insoluble substance/(%) ,≤ | 0.030 | 0.03 | 0.020 |
| Ash/(%) ,≤ | 0.020 | 0.020 | 0.020 |
The above is only the preferred embodiment of the present invention, it is noted that come for those skilled in the art
Saying, on the premise of without departing from the technology of the present invention principle, it is also possible to make some improvement and replacement, these improve and replace also should
It is considered as protection scope of the present invention.
Claims (8)
1. the method directly being prepared disproportionated rosin with iodine for catalyst by Colophonium, it is characterised in that the method includes:
Colophonium is put into Sedimentation tank, with conveying worm, Colophonium is delivered to dissolvers and dissolve, during dissolving, add Oleum Terebinthinae and water, molten
Xie Shitong enters steam, and temperature controls at 90-95 DEG C；The fat liquid dissolved is after the defecator in dissolvers removes thick impurity
Enter defecator;
Being passed through protection gas, the fat liquid of dissolving stands 6-8 hour in defecator, makes fat liquid and water self exfoliation, clean after clarification
Fat liquid processed is sent to reactor directly as the raw material of dismutation reaction;
In the environment of protection gas, reactor is warmed up to 250-270 DEG C, is incubated 30-60 minute;
Maintain protection compression ring border, temperature of reactor is down to less than 160 DEG C, is slowly added into iodine ceramsite catalyst, described iodine haydite
Prepare in iodine catalyst is attached to porous ceramic grain surface and micropore by catalyst;
Maintain protection compression ring border, be warmed up to 280 DEG C-290 DEG C, be incubated 120-240 minute;
Reduce temperature, and be filtered to remove the catalyst being mixed with in product when product is in liquid, i.e. prepare disproportionated rosin.
The method preparing disproportionated rosin the most as claimed in claim 1, it is characterised in that the gross mass of described Oleum Terebinthinae and water is
0.5～0.7 times of Colophonium quality;Described Oleum Terebinthinae is 1:1～1:3 with the mass volume ratio of water.
The method preparing disproportionated rosin the most as claimed in claim 1, it is characterised in that evaporate in described Colophonium course of dissolution
The Oleum Terebinthinae and the steam that come are reclaimed by the condenser of dissolver.
The method preparing disproportionated rosin the most as claimed in claim 1, it is characterised in that the water of described defecator effusion and Lignum Pini Nodi
The steam of oil enters condenser and reclaims, and slag-water slurry is discharged.
The method preparing disproportionated rosin the most according to claim 1, it is characterised in that: described iodine ceramsite catalyst is a diameter of
0.1-1mm。
The method preparing disproportionated rosin the most according to claim 1, it is characterised in that: described protection gas be noble gas or
Nitrogen.
The method preparing disproportionated rosin the most according to claim 1, it is characterised in that: step 3) in, mixing speed is 300
～500 turns/min.
The method preparing disproportionated rosin the most according to claim 1, it is characterised in that: described step 6) in, temperature reduces
To 200～250 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610267032.7A CN105778771A (en) | 2016-04-27 | 2016-04-27 | Method for directly preparing disproportionated rosin from rosin through taking iodine as catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610267032.7A CN105778771A (en) | 2016-04-27 | 2016-04-27 | Method for directly preparing disproportionated rosin from rosin through taking iodine as catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105778771A true CN105778771A (en) | 2016-07-20 |
Family
ID=56399529
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610267032.7A Pending CN105778771A (en) | 2016-04-27 | 2016-04-27 | Method for directly preparing disproportionated rosin from rosin through taking iodine as catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105778771A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105051A (en) * | 1994-08-08 | 1995-07-12 | 唐亚贤 | Method for producing disproportionated rosin by using pine gum as raw material |
| CN1616570A (en) * | 2004-09-27 | 2005-05-18 | 广西大学 | Method for producing pale disproportionated rosin with high content dehydroabietic acid and P-camphogen simultinuously |
| CN104342034A (en) * | 2013-07-24 | 2015-02-11 | 琼中森富松香加工厂有限公司 | Rosin production technology process |
| CN105111940A (en) * | 2015-09-23 | 2015-12-02 | 广西科茂林化有限公司 | Disproportionated rosin and preparation method thereof |
-
2016
- 2016-04-27 CN CN201610267032.7A patent/CN105778771A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105051A (en) * | 1994-08-08 | 1995-07-12 | 唐亚贤 | Method for producing disproportionated rosin by using pine gum as raw material |
| CN1616570A (en) * | 2004-09-27 | 2005-05-18 | 广西大学 | Method for producing pale disproportionated rosin with high content dehydroabietic acid and P-camphogen simultinuously |
| CN104342034A (en) * | 2013-07-24 | 2015-02-11 | 琼中森富松香加工厂有限公司 | Rosin production technology process |
| CN105111940A (en) * | 2015-09-23 | 2015-12-02 | 广西科茂林化有限公司 | Disproportionated rosin and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 刘培生: "《多孔材料引论》", 31 December 2012, 清华大学出版社 * |
| 杨东海: "《松香在加工及利用》", 30 April 1984, 中国林业出版社 * |
| 罗民华: "《多孔陶瓷使用技术》", 31 March 2006, 中国建筑工业出版社 * |
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Application publication date: 20160720 |
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