CN101402596A - Process for producing thiourea dioxide water solution - Google Patents
Process for producing thiourea dioxide water solution Download PDFInfo
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- CN101402596A CN101402596A CNA2008101601325A CN200810160132A CN101402596A CN 101402596 A CN101402596 A CN 101402596A CN A2008101601325 A CNA2008101601325 A CN A2008101601325A CN 200810160132 A CN200810160132 A CN 200810160132A CN 101402596 A CN101402596 A CN 101402596A
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- CN
- China
- Prior art keywords
- thiourea
- thiourea dioxide
- aqueous solution
- oxyful
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 11
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 19
- 238000004076 pulp bleaching Methods 0.000 abstract description 8
- 229920001131 Pulp (paper) Polymers 0.000 abstract description 6
- 238000001816 cooling Methods 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000007853 buffer solution Substances 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000012530 fluid Substances 0.000 abstract 1
- 238000010517 secondary reaction Methods 0.000 abstract 1
- 238000004061 bleaching Methods 0.000 description 9
- -1 thiourea peroxide Chemical class 0.000 description 9
- 238000009835 boiling Methods 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000003139 buffering effect Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000002761 deinking Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000010893 paper waste Substances 0.000 description 2
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 2
- 239000003352 sequestering agent Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- NYYSPVRERVXMLJ-UHFFFAOYSA-N 4,4-difluorocyclohexan-1-one Chemical compound FC1(F)CCC(=O)CC1 NYYSPVRERVXMLJ-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
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- Paper (AREA)
Abstract
The invention provides a method for preparing thiourea dioxide aqueous solution for paper pulp bleaching, which is characterized in that a great amount of water is added when thiourea dioxide is prepared, cooling, crystallizing, filtering, drying and other steps are omitted to directly prepare the thiourea dioxide aqueous solution used for the paper pulp bleaching. Because the reaction mechanism of the preparation is complicated, the control of the temperature and the pH value of a system is key. The preparation is realized as follows: (1) the reaction between thiourea and oxyful is a strong exothermic reaction with high pyrometric effect and uneasy control, first dropping speed of the oxyful must be well controlled, moreover, the volume of preset fluid is 60 times of the weight of the thiourea; (2) the pH value of a reaction system is maintained between 2 and 6 so as to reduce the occurrence of secondary reaction, and is stabilized by adding partial buffer solution into the thiourea and the oxyful; and (3) the ratio of the thiourea to the oxyful is 1 to 2.05. Yield of TD aqueous solution prepared by the method can reach about 90 percent. The method has the advantages of simple technology and little investment, and can produce the high-yield thiourea dioxide aqueous solution only by slightly improving the prior technology.
Description
Technical field:
The present invention relates to a kind of is raw material is realized the high yield thiourea peroxide of preparation (the being called for short TD) aqueous solution by the pH value that presets buffered soln stopping reaction system in reaction system method with thiocarbamide and hydrogen peroxide, the aqueous solution of its preparation is directly used in the bleaching of paper waste, to reduce bleaching cost.
Background technology:
At present, the traditional oxidation bleaching of the general employing of pulp from decoloured waste paper bleaching is as hypochlorite, H
2O
2, O
2Deng.The oxidized form SYNTHETIC OPTICAL WHITNER mainly is oxidative degradation and removes the residual lignin in the slurry and improve whiteness.Continuous development along with journalism, the kind of newspaper, printed form are also rich and varied, the reason that causes the old paper stock color development is more complicated also, in paper pulp the residual lignin, also may be need add the color that additive such as dyestuff generates owing to certain, and the printing-ink pigment particles of in deinking process, not removing as yet etc.Reduced form bleaching is by reducing the chromophoric group of fiber itself, slough the color of dyestuff effectively and improve whiteness, so the reduced form SYNTHETIC OPTICAL WHITNER is good discoloring agent that reduced form SYNTHETIC OPTICAL WHITNER commonly used comprises V-Brite B, thiourea peroxide etc.Wherein, the V-Brite B poor stability, easily oxidation and decomposition, use range is subjected to certain restriction; Thiourea peroxide (TD) claims formamidine sulfinic acid again, is difficult for decomposing in air, resolves into the extremely strong sulfoxylic acid of urea and reductibility in micro alkaline solution, and final resolvent is urea and vitriol; Thiourea peroxide is as the agent of a kind of novel environment friendly association with pulp bleaching, uses easy to operately, and bleaching effect is better.Use when having thiourea peroxide bleached pulp commonly used now generally all is the thiourea peroxide powder that generates by the water solvent method, its concrete preparation method is to be raw material with thiocarbamide and hydrogen peroxide, in reactor, react, make the thiourea peroxide solid by suction filtration, oven dry behind the crystallisation by cooling, when bleaching, again the aqueous solution is made in its dissolving.Need cooling, crystallization, drying etc. in this method for preparing the solid thiourea peroxide and the step, therefore, its complex process, cooling and drying process power consumption height, production cost is higher.
Summary of the invention:
The objective of the invention is to overcome the shortcoming that prior art exists, seeking a kind of is raw material with thiocarbamide and hydrogen peroxide, adopts the mode of the pH value that presets buffered soln stopping reaction system directly to prepare thiourea dioxide water solution.
To achieve these goals, the present invention is reactor with the four-hole boiling flask, earlier four-hole boiling flask is placed ice bath, and ethanol in the control bath and water mixture temperature are at-20 ℃～-15 ℃; In four-hole boiling flask, add distilled water and buffering solution again, when attemperation is 10 ℃, add thiocarbamide and begin and stir, when treating that again temperature drops to 0 ℃, begin to drip hydrogen peroxide, control reaction temperature is 0 ℃～10 ℃, hydrogen peroxide drips the back to be continued to stir, and treats that temperature reaches reaction end when no longer rising, and takes off four-hole boiling flask, promptly make the thiourea dioxide water solution product, its yield reaches 90%.
Both proportionings are 2: 1 in the mixture of the second alcohol and water in the above-mentioned preparation process in the bath; In four-hole boiling flask, add distilled water and buffering solution; Choose HOAc-NaOAc and make buffered soln; The adding weight ratio of thiocarbamide and hydrogen peroxide is 1: 2～2.1.
The present invention compared with prior art, when the preparation thiourea peroxide, add big yield, add the pH value of buffered soln stopping reaction system, thereby directly be prepared into thiourea dioxide water solution, do not need cooling, crystallization and drying step, its technological principle is reliable, and step is simple, product yield height, save energy and production cost.
Embodiment:
Be described further below in conjunction with embodiment.
Example 1: the product yield situation that presets the different ratios of distilled water and buffered soln
Present embodiment places ice bath with four-hole boiling flask earlier, and ethanol in the control bath and water mixture temperature are at-20 ℃～-15 ℃; In four-hole boiling flask, add distilled water and buffering solution again in the Different Weight ratio, when attemperation is 10 ℃, add 1 gram thiocarbamide and begin stirring, when treating that again temperature drops to 0 ℃, begin to drip 2～2.1 gram hydrogen peroxide, 5 ℃ of control reaction temperature, hydrogen peroxide drips the back to be continued to stir, and treats to take off four-hole boiling flask when temperature no longer rises, and promptly makes thiourea dioxide water solution product 60ml, its yield reaches 90%, concrete data and the results are shown in Table 1.
Data by table 1 find that buffered soln is more remarkable to the yield influence of preparation sulfurous gas urea solution, and when the ratio that presets distilled water and buffering solution was 1: 1, yield was up to 90.38%, best results.
Example 2: thiourea dioxide water solution compares the influence of association with pulp bleaching colourity.
Be used for association with pulp bleaching with only adding the thiourea dioxide water solution that buffered soln makes with the thiourea dioxide water solution that different sequestrants, buffered soln make respectively, more as shown in table 2 with former wood pulp bleaching results.
As seen from Table 2, the TD aqueous solution is used for association with pulp bleaching, and lightness index L* raises to some extent, and chromaticity index a* reduces b* and increases, and illustrates that the TD aqueous solution is effective SYNTHETIC OPTICAL WHITNER to disregard message paper deinking slurry, is again good discoloring agent; The adding of sequestrant can obviously improve the bleaching effect of paper pulp, and the TD sodium hypochlorite solution bleaching effect that adding STPP makes is best.
Table 1: the yield situation of four enforcements of the distilled water of different ratios and buffering solution.
| The test sequence number | 1 | 2 | 3 | 4 |
| Buffered soln/distilled water | 0∶1 | 1∶1 | 3∶1 | 1∶0 |
| Yield % | 83.20 | 90.38 | 84.94 | 89.73 |
Table 2: thiourea dioxide water solution is to the situation that influences of association with pulp bleaching colourity.
| L | a* | b* | ISO | |
| Former wood pulp | 88.42 | 0.26 | -1.78 | 71.25 |
| Buffer reagent | 89.34 | 0.2 | -0.78 | 76.11 |
| DTPA (delaying) | 89.81 | 0.35 | -2.07 | 78.62 |
| STPP (delaying) | 90.12 | 0.17 | -0.85 | 78.87 |
| EDTA (delaying) | 89.96 | 0.34 | -1.82 | 78.67 |
Claims (4)
1, a kind of preparation method of high yield thiourea dioxide aqueous solution, its process characteristic: with thiocarbamide and hydrogen peroxide is that the pH value that raw material is taked to preset buffered soln stopping reaction system makes thiourea dioxide water solution, and its preset value is 60 times of thiocarbamide weight.
2, system temperature is controlled at 0～10 ℃ in preparation thiourea dioxide water solution process.
3, the ratio of thiocarbamide and hydrogen peroxide is 1: 2.05.
4, as described in the right 1,2,3, the thiourea dioxide water solution yield of preparation can reach more than 90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101601325A CN101402596A (en) | 2008-11-14 | 2008-11-14 | Process for producing thiourea dioxide water solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101601325A CN101402596A (en) | 2008-11-14 | 2008-11-14 | Process for producing thiourea dioxide water solution |
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| Publication Number | Publication Date |
|---|---|
| CN101402596A true CN101402596A (en) | 2009-04-08 |
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ID=40536779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008101601325A Pending CN101402596A (en) | 2008-11-14 | 2008-11-14 | Process for producing thiourea dioxide water solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101402596A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4233238A (en) * | 1978-07-25 | 1980-11-11 | Tokai Denka Kogyo Kabushiki Kaisha | Process for preparing thiourea dioxide |
| US4235812A (en) * | 1978-07-25 | 1980-11-25 | Tokai Denka Kogyo Kabushiki Kaisha | Process for preparing thiourea dioxide |
| CN101195972A (en) * | 2006-12-05 | 2008-06-11 | 天津科技大学 | In situ preparation method of thiourea dioxide in paper-pulp decolorization |
-
2008
- 2008-11-14 CN CNA2008101601325A patent/CN101402596A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4233238A (en) * | 1978-07-25 | 1980-11-11 | Tokai Denka Kogyo Kabushiki Kaisha | Process for preparing thiourea dioxide |
| US4235812A (en) * | 1978-07-25 | 1980-11-25 | Tokai Denka Kogyo Kabushiki Kaisha | Process for preparing thiourea dioxide |
| CN101195972A (en) * | 2006-12-05 | 2008-06-11 | 天津科技大学 | In situ preparation method of thiourea dioxide in paper-pulp decolorization |
Non-Patent Citations (2)
| Title |
|---|
| 古绪鹏，周远友: "二氧化硫脲的制备及其在有机合成中的应用", 《化学研究与应用》 * |
| 汤秀华等: "二氧化硫脲工艺条件优化研究", 《四川理工学院学报（自然科学版）》 * |
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| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
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| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20090408 |