CN102381949B - Low-conversion-rate high-yield formaldehyde production technology and device thereof - Google Patents
Low-conversion-rate high-yield formaldehyde production technology and device thereof Download PDFInfo
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- CN102381949B CN102381949B CN 201110256397 CN201110256397A CN102381949B CN 102381949 B CN102381949 B CN 102381949B CN 201110256397 CN201110256397 CN 201110256397 CN 201110256397 A CN201110256397 A CN 201110256397A CN 102381949 B CN102381949 B CN 102381949B
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- formaldehyde
- dealcoholysis
- absorption tower
- methyl alcohol
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 201
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 238000005516 engineering process Methods 0.000 title claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 228
- 238000010521 absorption reaction Methods 0.000 claims abstract description 62
- 239000007789 gas Substances 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003063 flame retardant Substances 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 22
- 239000003570 air Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 13
- 230000007306 turnover Effects 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 238000006392 deoxygenation reaction Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000013589 supplement Substances 0.000 claims description 3
- 239000006200 vaporizer Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
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Abstract
The invention relates to the field of formaldehyde production technology, in particular to a low-conversion-rate high-yield formaldehyde production technology and device thereof. Reaction of ternary mixture with excessive methanol under action of catalyst is completed by controlling proportion of methanol in the ternary mixture, generated formaldehyde gas and other gases are cooled suddenly and fed into a primary absorption tower to be absorbed through process water, methanol-contained formaldehyde solution acquired from the primary absorption tower enters a first methanol removing device to be heated, methanol is removed in a gaseous state, the formaldehyde solution with methanol removed is used as finished formaldehyde products to be stored, the gaseous methanol removed by the first methanol removing device still contains formaldehyde in a small quantity so as to be fed into a secondary absorption tower to be absorbed and enter a second methanol removing device for removing methanol again, and the removed gaseous methanol enters a flame-retardant filter to enter a formaldehyde production system again for recycling reaction. The low-conversion-rate high-yield formaldehyde production technology has the advantages of low conversion rate, fewer negative reactions, low oxygen temperature control, long lifetime of catalyst, high yield and low material consumption.
Description
Technical field
The present invention relates to the production technique field of formaldehyde, especially a kind of low turnover ratio, high yield formaldehyde production technology and device thereof.
Background technology
At present, the China silver method Formaldehyde Production was through more than 50 years courses of trials and hardship, all obtained in every respect great achievement, energy consumption is the air feed type from consumption gas type changes into, material consumption is 445kg methyl alcohol/T 37% formaldehyde till now from 500kg methyl alcohol/T 37% formaldehyde, production capacity develops into more than 2,000 ten thousand tons of today from the hundreds of thousands of ton, and silver-colored method production production capacity and technology have been in rank first.Formaldehyde Production develops into by extensive style the production that becomes more meticulous, and by simply, to the road of career development, in technique and operation, research is exactly to improve turnover ratio.Present many factories manage in Formaldehyde Production, the formaldehyde process optimization, and catalyst is selected and is installed all and do well, but the material consumption level can only remain on the 445kg left and right.
Domestic Formaldehyde Production mainly adopts two kinds of operational paths, traditional technology and circulation of tail gas method technique, traditional technology is to produce formaldehyde by the ternary gas oxidizing reaction, circulation of tail gas method technique is to adopt quaternary gas oxidizing reaction to produce formaldehyde, reactive absorption mechanism is basic identical, just the configuration of reaction member equipment configuration is different, circulation of tail gas method technique increases exhaust system, with tail gas, replace part ingredient water steam to remove reaction heat, can accomplish 50% left and right concentration formaldehyde products, and two kinds of preparation method's pursuits is all to improve the transformation efficiency selectivity, all using Formaldehyde Production as systems engineering, make every effort to equipment, electric, instrument, starting material, operation and each unit of personnel, link is accomplished meticulous, reach high conversion.Above way can not reduce negative reaction simultaneously and guarantee not reduce productive rate at the raising transformation efficiency.
Summary of the invention
The technical problem to be solved in the present invention is: a kind of low turnover ratio, high yield formaldehyde production technology and device thereof are provided, reduce negative reaction, improve productive rate.
The technical solution adopted for the present invention to solve the technical problems is: a kind of low turnover ratio, the high yield prepn. of formaldehyde, control methyl alcohol, the ratio of methyl alcohol in the ternary mixture of air and water vapor, make the ternary mixture carry out alcohol excessive methanol oxidation and deoxygenation under catalyst action, formaldehyde gas after generation and other gas carry out quenching, then passing into first grade absorption tower is absorbed by process water, the formaldehyde solution that contains methyl alcohol of first grade absorption tower extraction enters in the first dealcoholysis device solution is heated, methyl alcohol is deviate from gaseous form, aldehyde solution after dealcoholysis is as the folding and unfolding of formaldehyde finished product, still contain a small amount of aldehyde in the gaseous methanol of deviating from the first dealcoholysis device, it is passed into to two-level absorption tower carries out after absorption operation entering in the second dealcoholysis device again carrying out dealcoholysis, the gaseous methanol of deviating from enters fire-retardant filter, reenter the Formaldehyde Production system and carry out the recycle reaction.
Preparation technology is as follows
(1) methyl alcohol and air are that ratio below 0.36 is mixed according to oxygen alcohol mol ratio;
(2) the binary mixture of methyl alcohol and air heated, the mixture after heating is removed to droplet;
(3) add saturated vapor in the mixture of methyl alcohol and air;
(4) the ternary mixture of methyl alcohol, air and water vapor heated, be heated between 100 ℃～120 ℃, then carried out the back-fire relief filtration;
(5) the ternary mixture passes into the oxidizer that catalyzer is housed, and mixture carries out oxidation and the deoxygenation of methyl alcohol under the high temperature of 590 ℃～610 ℃, generates formaldehyde gas;
(6) formaldehyde gas and other gas after the generation carries out quenching, then passing into first grade absorption tower is absorbed by process water, the formaldehyde solution that contains methyl alcohol of first grade absorption tower extraction enters in the first dealcoholysis device solution is heated, and methyl alcohol is deviate from gaseous form;
(7) the aldehyde solution after dealcoholysis is as the folding and unfolding of formaldehyde finished product, still contain a small amount of aldehyde in the gaseous methanol of deviating from the first dealcoholysis device, it is passed into to two-level absorption tower and carry out absorption operation, in rare aldehyde liquid after absorption, a part is carried out self-circulation in two-level absorption tower, another part liquid as a supplement enters first grade absorption tower, and other enter the second dealcoholysis device.
(8) the rare aldehyde solution taken out containing methyl alcohol in two-level absorption tower again carries out dealcoholysis in the second dealcoholysis device, the gaseous methanol of deviating from enters fire-retardant filter, reenter the Formaldehyde Production system and carry out the recycle reaction, water is got back to the two-level absorption tower hypomere and is done the circulation fluid absorption that circulates, and unabsorbed tail gas is sent into treater and burnt and emit heat.
A kind of low turnover ratio, the high yield formaldehyde production device, comprise vaporizer, fire-retardant filter, be incorporated with the oxidizer of catalyzer, first grade absorption tower and two-level absorption tower, at first grade absorption tower, with a dealcoholysis device, be connected, the first dealcoholysis device is connected with the secondary formaldehyde absorbing tower, the secondary formaldehyde absorbing tower is connected with the second dealcoholysis device, the formaldehyde solution that contains methyl alcohol of first grade absorption tower extraction enters in the first dealcoholysis device solution is heated, methyl alcohol is deviate from gaseous form, aldehyde solution after dealcoholysis is as the folding and unfolding of formaldehyde finished product, still contain a small amount of aldehyde in the gaseous methanol of deviating from the first dealcoholysis device, it is passed into to two-level absorption tower carries out after absorption operation entering in the second dealcoholysis device again carrying out dealcoholysis, the gaseous methanol of deviating from enters fire-retardant filter, reenter the Formaldehyde Production system and carry out the recycle reaction.
The structure of first and second dealcoholysis device is: comprise a cylindrical shell, there is solution entrance, taphole and pneumatic outlet on cylindrical shell, the heating tube that solution is wherein heated is set in cylindrical shell, the solution that contains methyl alcohol and formaldehyde enters in the dealcoholysis device solution is heated by the solution entrance, methyl alcohol is deviate from gaseous form by pneumatic outlet, and the solution after dealcoholysis is discharged by taphole.
The invention has the beneficial effects as follows: 1. formaldehyde prepration process of the present invention, because alcohol is excessive, turnover ratio is low, simultaneously formaldehyde reenters the Formaldehyde Production system by fire-retardant filter after deviating from gas form by the dealcoholysis device and carries out the recycle reaction, so Formaldehyde Production, oxygen temperature control are low, negative reaction is few, to the system interference factor, require low, reduced operation easier, reduced the unit consumption of methyl alcohol, the unit consumption of methyl alcohol of the present invention is 435kg/T; 2. under low turnover ratio, the driving cycle of equipment is long, and systemic resistance is little, and power consumption, energy consumption are low, and the catalyst life cycle is long; 3. formaldehyde products, through two sections dealcoholysis operations, can reach without pure requirement containing pure amount in product, and the quality of formaldehyde products is high; 4. stop frequency is few, and on consuming methyl alcohol without impact, material consumption is low; 5. make in tail gas CO content only 0.3%, CO
2content only 2.0%, in formaldehyde, pure content is without, formic acid content≤0.01.
The accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is further described.
Fig. 1 is process flow sheet of the present invention;
Fig. 2 is structure diagram of the present invention;
Fig. 3 is the structural representation of dealcoholysis device of the present invention;
1. first dealcoholysis devices in figure, 2. first grade absorption tower, 3. two-level absorption tower, 4. the second dealcoholysis device, 5. recycle pump, 6. fire-retardant filter, 7. cylindrical shell, 8. heating tube.
Embodiment
With preferred embodiment, the present invention is further detailed explanation by reference to the accompanying drawings now.These accompanying drawings are the schematic diagram of simplification, basic structure of the present invention only is described in a schematic way, so it only show the formation relevant with the present invention.
As shown in Figure 2, a kind of low turnover ratio, the high yield formaldehyde production device, comprise vaporizer, fire-retardant filter 6, be incorporated with the oxidizer of catalyzer, first grade absorption tower 2 and two-level absorption tower 3, at first grade absorption tower 2, with a dealcoholysis device, be connected, the first dealcoholysis device 1 is connected with the secondary formaldehyde absorbing tower, the secondary formaldehyde absorbing tower is connected with the second dealcoholysis device 4, the formaldehyde solution that contains methyl alcohol of first grade absorption tower 2 extraction enters in the first dealcoholysis device 1 solution is heated, methyl alcohol is deviate from gaseous form, aldehyde solution after dealcoholysis is as the folding and unfolding of formaldehyde finished product, still contain a small amount of aldehyde in the gaseous methanol of deviating from the first dealcoholysis device 1, it is passed into to two-level absorption tower 3 carries out after absorption operation entering in the second dealcoholysis device 4 again carrying out dealcoholysis, the gaseous methanol of deviating from enters fire-retardant filter 6, reenter the Formaldehyde Production system and carry out the recycle reaction.Realize driving, the circulation of solution and water between each parts by recycle pump 5.
The installation site of first and second dealcoholysis device is not particularly limited, can arrange separately, or in conjunction with in existing installation, as shown in Figure 3 be wherein a kind of form of this kind of dealcoholysis device, can also adopt other similar indirect heating modes.The structure of first and second dealcoholysis device is: comprise a cylindrical shell 7, there is solution entrance, taphole and pneumatic outlet on cylindrical shell 7, at the interior heating tube 8 that solution is wherein heated that arranges of cylindrical shell 7, the solution that contains methyl alcohol and formaldehyde enters in the dealcoholysis device solution is heated by the solution entrance, methyl alcohol is deviate from gaseous form by pneumatic outlet, and the solution after dealcoholysis is discharged by taphole.
The formaldehyde prepration process of preferred forms as shown in Figure 1, its technological process is as follows
(1) methyl alcohol and air are that ratio below 0.36 is mixed according to oxygen alcohol mol ratio;
(2) the binary mixture of methyl alcohol and air heated, the mixture after heating is removed to droplet;
(3) add saturated vapor in the mixture of methyl alcohol and air;
(4) the ternary mixture of methyl alcohol, air and water vapor heated, be heated between 100 ℃～120 ℃, then carried out the back-fire relief filtration;
(5) the ternary mixture passes into the oxidizer that catalyzer is housed, and mixture carries out oxidation and the deoxygenation of methyl alcohol under the high temperature of 590 ℃～610 ℃, generates formaldehyde gas;
(6) formaldehyde gas and other gas after the generation carries out quenching, prevents from carrying out thermolysis, then by process water, is absorbed, and the finished product of extraction passes through indirect heating, the first dealcoholysis device of separation function is arranged.
(7) aldehyde after the separation is as the folding and unfolding of formaldehyde finished product, and gaseous methanol and a small amount of aldehyde go two-level absorption tower 3 to carry out absorption operation.In rare aldehyde liquid after absorption, a part is carried out self-circulation in two-level absorption tower, and another part liquid as a supplement enters first grade absorption tower, and other enter the second dealcoholysis device.
(8) the rare aldehyde solution taken out containing methyl alcohol in two-level absorption tower again carries out dealcoholysis in the second dealcoholysis device, and gas methyl alcohol removes fire-retardant filter 6, enters the Formaldehyde Production system and carries out the recycle reaction.Water is got back to two-level absorption tower 3 hypomeres and is done the circulation fluid absorption that circulates.Unabsorbed tail gas is sent into treater and is burnt and emit heat, indirectly produces steam, and steam can be for outside.In the second dealcoholysis device, the content of formaldehyde is very low, and in heat-processed, formaldehyde can not volatilize, and only having methyl alcohol can be deviate from.
The above-mentioned foundation desirable embodiment of the present invention of take is enlightenment, and by above-mentioned description, the relevant staff can, in the scope that does not depart from this invention technological thought, carry out various change and modification fully.The technical scope of this invention is not limited to the content on specification sheets, must determine its technical scope according to the claim scope
Claims (3)
1. a low turnover ratio, the high yield prepn. of formaldehyde, it is characterized in that: control methyl alcohol, the ratio of methyl alcohol in the ternary mixture of air and water vapor, make the ternary mixture carry out alcohol excessive methanol oxidation and deoxygenation under catalyst action, formaldehyde gas after generation and other gas carry out quenching, then passing into first grade absorption tower is absorbed by process water, the formaldehyde solution that contains methyl alcohol of first grade absorption tower extraction enters in the first dealcoholysis device solution is heated, methyl alcohol is deviate from gaseous form, aldehyde solution after dealcoholysis is as the folding and unfolding of formaldehyde finished product, still contain a small amount of aldehyde in the gaseous methanol of deviating from the first dealcoholysis device, it is passed into to two-level absorption tower carries out after absorption operation entering in the second dealcoholysis device again carrying out dealcoholysis, the gaseous methanol of deviating from enters fire-retardant filter, reenter the Formaldehyde Production system and carry out the recycle reaction,
Preparation technology is as follows:
(1) methyl alcohol and air are that ratio below 0.36 is mixed according to oxygen alcohol mol ratio;
(2) the binary mixture of methyl alcohol and air heated, the mixture after heating is removed to droplet;
(3) add saturated vapor in the mixture of methyl alcohol and air;
(4) the ternary mixture of methyl alcohol, air and water vapor heated, be heated between 100 ℃～120 ℃, then carried out the back-fire relief filtration;
(5) the ternary mixture passes into the oxidizer that catalyzer is housed, and mixture carries out oxidation and the deoxygenation of methyl alcohol under the high temperature of 590 ℃～610 ℃, generates formaldehyde gas;
(6) formaldehyde gas and other gas after the generation carries out quenching, then passing into first grade absorption tower is absorbed by process water, the formaldehyde solution that contains methyl alcohol of first grade absorption tower extraction enters in the first dealcoholysis device solution is heated, and methyl alcohol is deviate from gaseous form;
(7) the aldehyde solution after dealcoholysis is as the folding and unfolding of formaldehyde finished product, still contain a small amount of aldehyde in the gaseous methanol of deviating from the first dealcoholysis device, it is passed into to two-level absorption tower and carry out absorption operation, in rare aldehyde liquid after absorption, a part is carried out self-circulation in two-level absorption tower, another part liquid as a supplement enters first grade absorption tower, and other enter the second dealcoholysis device;
(8) the rare aldehyde solution taken out containing methyl alcohol in two-level absorption tower again carries out dealcoholysis in the second dealcoholysis device, the gaseous methanol of deviating from enters fire-retardant filter, reenter the Formaldehyde Production system and carry out the recycle reaction, water is got back to the two-level absorption tower hypomere and is done the circulation fluid absorption that circulates, and unabsorbed tail gas is sent into treater and burnt and emit heat.
2. a low turnover ratio, the high yield formaldehyde production device, comprise vaporizer, fire-retardant filter, be incorporated with the oxidizer of catalyzer, first grade absorption tower and two-level absorption tower, it is characterized in that: at described first grade absorption tower, with the first dealcoholysis device, be connected, the first dealcoholysis device is connected with two-level absorption tower, two-level absorption tower is connected with the second dealcoholysis device, the formaldehyde solution that contains methyl alcohol of first grade absorption tower extraction enters in the first dealcoholysis device solution is heated, methyl alcohol is deviate from gaseous form, aldehyde solution after dealcoholysis is as the folding and unfolding of formaldehyde finished product, still contain a small amount of aldehyde in the gaseous methanol of deviating from the first dealcoholysis device, it is passed into to two-level absorption tower carries out after absorption operation entering in the second dealcoholysis device again carrying out dealcoholysis, the gaseous methanol of deviating from enters fire-retardant filter, reenter the Formaldehyde Production system and carry out the recycle reaction.
3. low turnover ratio according to claim 2, high yield formaldehyde production device, it is characterized in that: the structure of described first and second dealcoholysis device is: comprise a cylindrical shell, there is solution entrance, taphole and pneumatic outlet on cylindrical shell, the heating tube that solution is wherein heated is set in cylindrical shell, the solution that contains methyl alcohol and formaldehyde enters in the dealcoholysis device solution is heated by the solution entrance, methyl alcohol is deviate from gaseous form by pneumatic outlet, and the solution after dealcoholysis is discharged by taphole.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1473811A (en) * | 2003-08-05 | 2004-02-11 | 洪海玲 | Method for producing low alcohol, high concentration formaldehyde |
| CN101508633A (en) * | 2009-03-24 | 2009-08-19 | 江苏恒茂机械制造有限公司 | Process and apparatus for preparing methanal with low transformational cycle method |
| CN101550073A (en) * | 2009-05-12 | 2009-10-07 | 范轩羽 | Equipment for producing high concentration dealcoholization formaldehyde and production technology thereof |
| CN202246481U (en) * | 2011-08-31 | 2012-05-30 | 江苏恒茂机械制造有限公司 | Formaldehyde production device with low conversion rate and high yield |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1473811A (en) * | 2003-08-05 | 2004-02-11 | 洪海玲 | Method for producing low alcohol, high concentration formaldehyde |
| CN101508633A (en) * | 2009-03-24 | 2009-08-19 | 江苏恒茂机械制造有限公司 | Process and apparatus for preparing methanal with low transformational cycle method |
| CN101550073A (en) * | 2009-05-12 | 2009-10-07 | 范轩羽 | Equipment for producing high concentration dealcoholization formaldehyde and production technology thereof |
| CN202246481U (en) * | 2011-08-31 | 2012-05-30 | 江苏恒茂机械制造有限公司 | Formaldehyde production device with low conversion rate and high yield |
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