A foam inhibitor with tall oil soap separation function
By preparing a tall oil soap separation additive that combines waxy substances with mineral oil and silica, the problems of low tall oil soap recovery rate and insufficient defoaming performance were solved, achieving efficient tall oil soap recovery and defoaming effects and reducing production costs.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- YANGZHOU SIXIN NEW MATERIAL TECH CO LTD
- Filing Date
- 2022-12-26
- Publication Date
- 2026-06-30
AI Technical Summary
In existing papermaking pulping processes, tall oil soap has a low recovery rate and insufficient defoaming performance, leading to evaporator fouling, scaling, and foaming that affect production. Existing defoamers are either ineffective at high temperatures or have high costs and poor fluidity.
A tall oil soap separating additive that also has defoaming properties was prepared by combining waxes with mineral oil and silica, along with end-capped polyethers and fatty alcohol polyethers and chiral monoterpene alcohols in the synergist.
It improves the recovery rate and defoaming performance of tall oil soap, solves the foaming problem at high temperatures, and reduces production costs.
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Abstract
Description
Technical Field
[0001] This patent relates to a tall oil soap separating additive. More precisely, it relates to a tall oil soap separating additive for use in the papermaking industry that also has defoaming properties. It is a fine chemical additive, and therefore, this invention belongs to the field of fine chemical formulation technology. Background Technology
[0002] In the papermaking pulping process, sulfate pulping is one of the common preparation methods. After pulping, recovering tall oil soap from the pulping waste liquor is an important operation unit in the pulping process. This is because tall oil soap can be further processed and fractionated to form tall oil fatty acids, resin acids and phytosterols. These substances can be further derived to form a variety of surfactants, which are widely used in cosmetics, inks and coatings. Besides the recycling value of tall oil soap, it also causes problems such as evaporator fouling and scaling, asphalt formation, the need for bleaching chemicals, foaming in the paper machine, and blackening in the recycling furnace during sulfate recovery and subsequent papermaking processes. Furthermore, in the papermaking pulping process, the presence of a large amount of surfactants in the black liquor easily generates foam, severely affecting normal production and operation. Defoaming substances need to be added to control the foam. Patent CN200880002230.4 introduces a polyether with a specific structure as a separation aid for tall oil soap in black liquor. However, because polyether itself has poor defoaming ability, it can only improve the removal efficiency of tall oil in the black liquor system without simultaneously addressing defoaming and foam suppression performance. Therefore, further improvements are needed. US4976888 describes an emulsion-type defoamer composed of fatty alcohols, fatty acid esters, hydrocarbons, or fatty acids. However, this defoamer is ineffective at high temperatures and does not significantly improve the extraction of tall oil soaps from black liquor. CN200810012582 describes a defoamer for papermaking black liquor mainly composed of kerosene, paraffin wax, octyl, and sulfonated castor oil. However, this type of defoamer, due to its high paraffin content, is not only costly but also has poor flowability, high viscosity, and fails to meet the required defoaming and foam-suppressing performance. CN201510096290.9 discloses a defoamer prepared by introducing two end-capped polyethers stepwise into a mineral oil carrier for synergistic effects. This defoamer possesses defoaming properties and also helps improve the removal rate of tall oil soaps in papermaking black liquor; however, the separation rate of tall oil soaps needs further improvement. Summary of the Invention
[0003] The purpose of this invention is to provide a tall oil soap separation additive that also has defoaming properties. It improves the defoaming performance by combining waxes with mineral oil and silica. The end-capped polyether and the fatty alcohol polyether and chiral monoterpene alcohol in the synergist work together to improve the recovery rate of tall oil soap. Finally, a separation additive that has a good effect on removing tall oil soap and also has defoaming properties is prepared.
[0004] The tall oil soap separating additive that also has defoaming properties is composed of the following components:
[0005] (1) Mineral oil, a compound composed of carbon and hydrogen atoms. It is selected from kerosene, diesel, engine oil, machine oil, white oil, liquid wax, alkylbenzene, naphthenic oil, and heavy alkylbenzene, and can be used alone or in combination. The amount of mineral oil used is 70-85% of the total mass of the defoamer.
[0006] (2) Silicone polyether, with the following structural formula:
[0007] (CH3)3SiO{ ((CH3)2SiO) x (CH3GSiO) y}(CH3)2G
[0008] The subscript x is an integer from 10 to 200; y is an integer from 5 to 30; G is a polyether group with the structural formula: -(CH2). z (EO) g (PO) h H, where the subscript z is an integer from 2 to 6, g is an integer from 20 to 100, and h is an integer from 1 to 20, and the dosage accounts for 5-15% of the total mass of the defoamer.
[0009] (3) Main defoaming substances, including waxes and silica, accounting for 1-8% of the total mass of the defoamer;
[0010] The waxes mentioned are selected from waxes with a melting point of 30-120℃, including natural waxes, synthetic waxes, mineral waxes, and petroleum waxes, and account for 10-40% of the total mass of the main defoaming substances.
[0011] The preferred form of silica is hydrophobic silica with a specific surface area of 30–500 m². 2 / g; the dosage accounts for 60-90% of the total mass of the main defoaming substances.
[0012] (4) Synergist, wherein the synergist is composed of fatty alcohol polyether and chiral monoterpene alcohol, wherein the amount of chiral monoterpene alcohol accounts for 20-50% of the total mass of the synergist; the amount of fatty alcohol polyether accounts for 50-80% of the total mass of the synergist; the chiral monoterpene alcohol is selected from rosin alcohol and menthol; the general structural formula of fatty alcohol polyether is R 3 (OCH2CH2) m (OCH2CHCH3) n OH, R 3 The synergist is a straight-chain or branched alkyl, cycloalkyl, or aralkyl group with 8-22 carbon atoms, where m is an integer from 1 to 50 and n is an integer from 10 to 100. Fatty alcohol polyethers and chiral monoterpene alcohols are stirred at 25°C to 100°C and kept at this temperature until the system becomes transparent and clear. The amount of synergist used is 5-15% of the total mass of the defoamer.
[0013] A method for preparing a tall oil soap separating additive that also has defoaming properties is as follows:
[0014] (1) First, add mineral oil, silicone polyether and the main defoaming substance into the reaction flask. After adding, stir and heat to 80-150℃ and keep warm for 0.5-3 hours.
[0015] (2) After the heat preservation is completed, cool down to 50-80℃, add the synergist, stir evenly and then homogenize the material;
[0016] (3) Vacuum degassing to obtain the foam inhibitor. Detailed Implementation
[0017] Synergist Examples
[0018]
[0019] Silicone polyether examples
[0020]
[0021] Example 1
[0022] 70g kerosene, 15g silicone polyether 1, 0.8g natural wax, and 7.2g of a substance with a specific surface area of 300m² were added. 2 / g of hydrophobic silica was added to the reaction flask, and after the addition was complete, the mixture was stirred and heated to 80-150℃ and kept at that temperature for 0.5-3h. After the temperature was kept at that temperature, the temperature was lowered to 50-80℃ and 7g of synergist 1 was added. The mixture was stirred evenly and the material was homogenized. Finally, the mixture was degassed under vacuum to obtain the foam inhibitor D1.
[0023] Example 2
[0024] Mix 85g of diesel fuel and engine oil, 5g of silicone polyether 2, 0.4g of synthetic wax, and 0.6g of a substance with a specific surface area of 30m². 2 / g of hydrophobic silica was added to the reaction flask, and after the addition was complete, the mixture was stirred and heated to 80-150℃ and kept at that temperature for 0.5-3h. After the temperature was kept at that temperature, the temperature was lowered to 50-80℃ and 9g of synergist 2 was added. The mixture was stirred evenly and the material was homogenized. Finally, the material was degassed under vacuum to obtain the foam inhibitor D2.
[0025] Example 3
[0026] Mix 80g of machine oil, 10g of silicone polyether 3, 2.5g of mineral wax, and 2.5g of a specific surface area of 100m². 2 / g of hydrophobic silica was added to the reaction flask, and after the addition was complete, the mixture was stirred and heated to 80-150℃ and kept at that temperature for 0.5-3h. After the temperature was kept at that temperature, the temperature was lowered to 50-80℃ and 5g of synergist 3 was added. The mixture was stirred evenly and the material was homogenized. Finally, the material was degassed under vacuum to obtain the foam inhibitor D3.
[0027] Example 4
[0028] 73g of white oil and naphthenic oil, 11g of silicone polyether 4, 0.5g of petroleum wax, and 0.5g of a specific surface area of 200m² were added. 2 / g of hydrophobic silica was added to the reaction flask, and after the addition was complete, the mixture was stirred and heated to 80-150℃ and kept at that temperature for 0.5-3h. After the temperature was kept at that temperature, the temperature was lowered to 50-80℃ and 15g of synergist 4 was added. The mixture was stirred evenly and the material was homogenized. Finally, the mixture was degassed under vacuum to obtain the foam inhibitor D4.
[0029] Example 5
[0030] Mix 80g liquid wax, 6g silicone polyether, 1g mineral wax, and 1g of a substance with a specific surface area of 60m². 2 / g of hydrophobic silica was added to the reaction flask, and after the addition was complete, the mixture was stirred and heated to 80-150℃ and kept at that temperature for 0.5-3h. After the temperature was kept at that temperature, the temperature was lowered to 50-80℃ and 12g of synergist 5 was added. The mixture was stirred evenly and the material was homogenized. Finally, the mixture was degassed under vacuum to obtain the foam inhibitor D5.
[0031] Example 6
[0032] 75g of alkylbenzene and heavy alkylbenzene, 8g of silicone polyether 6, 3g of natural wax, and 5g of a specific surface area of 250m² were added. 2 / g of hydrophobic silica was added to the reaction flask, and after the addition was complete, the mixture was stirred and heated to 80-150℃ and kept at that temperature for 0.5-3h. After the temperature was kept at that temperature, the temperature was lowered to 50-80℃ and 9g of synergist 6 was added. The mixture was stirred evenly and the material was homogenized. Finally, the mixture was degassed under vacuum to obtain the foam inhibitor D6.
[0033] Comparative Example 1
[0034] 70g kerosene, 15g silicone polyether, and 1.8g of a product with a specific surface area of 300m² were added. 2 / g of hydrophobic silica was added to the reaction flask, and after the addition was complete, the mixture was stirred and heated to 80-150℃ and kept at that temperature for 0.5-3h. After the temperature was kept at that temperature, the temperature was lowered to 50-80℃ and 7g of synergist 1 was added. The mixture was stirred evenly and the material was homogenized. Finally, the mixture was degassed under vacuum to obtain the foam inhibitor D7.
[0035] Comparative Example 2
[0036] Add 85g of diesel oil and engine oil, 5g of silicone polyether 2 and 1g of synthetic wax to the reaction flask. After the addition is complete, stir and heat to 80-150℃ and keep warm for 0.5-3h. After the heat preservation is completed, cool down to 50-80℃ and add 9g of synergist 2. Stir evenly and homogenize the material. Finally, degas under vacuum to obtain the foam inhibitor D8.
[0037] Comparative Example 3
[0038] 90g of machine oil, 2.5g of mineral wax, and 2.5g of a specific surface area of 100m² were mixed. 2 / g of hydrophobic silica was added to the reaction flask, and after the addition was complete, the mixture was stirred and heated to 80-150℃ and kept at that temperature for 0.5-3h. After the temperature was kept at that temperature, the temperature was lowered to 50-80℃ and 5g of synergist 3 was added. The mixture was stirred evenly and the material was homogenized. Finally, the material was degassed under vacuum to obtain the foam inhibitor D9.
[0039] Comparative Example 4
[0040] 73g of white oil and naphthenic oil, 11g of silicone polyether 4, 0.5g of petroleum wax, and 0.5g of a specific surface area of 200m² were added. 2 / g of hydrophobic silica was added to the reaction flask, and after the addition was complete, the mixture was stirred and heated to 80-150℃, and kept at this temperature for 0.5-3 hours. After the holding time was completed, the temperature was lowered to 50-80℃ and 15g of C was added. 15 H 31 (OCH2CH2)6(OCH2CHCH3) 30 After stirring evenly, the material is homogenized; finally, it is degassed under vacuum to obtain the foam inhibitor D10.
[0041] Comparative Example 5
[0042] Mix 80g liquid wax, 6g silicone polyether, 1g mineral wax, and 1g of a substance with a specific surface area of 60m². 2 / g of hydrophobic silica was added to the reaction flask, and after the addition was complete, the mixture was stirred and heated to 80-150℃ and kept at that temperature for 0.5-3h. After the temperature was kept at that temperature, the temperature was lowered to 50-80℃ and 12g of rosin alcohol was added. The mixture was stirred evenly and the material was homogenized. Finally, the material was degassed under vacuum to obtain the foam inhibitor D11.
[0043] Comparative Example 6
[0044] 75g of alkylbenzene and heavy alkylbenzene, 8g of silicone polyether 6, 3g of natural wax, and 5g of a specific surface area of 250m² were added. 2 / g of hydrophobic silica was added to the reaction flask, and after the addition was complete, the mixture was stirred and heated to 80-150℃ and kept at that temperature for 0.5-3h. After the temperature was kept at that temperature, the temperature was lowered to 50-80℃ and 9g of oleic acid polyoxyethylene ether was added. The mixture was stirred evenly and then homogenized. Finally, the mixture was degassed under vacuum to obtain the foam inhibitor D12.
[0045] Comparative Example 7
[0046] D13 was prepared according to Example 1 in patent ZL201510096290.9.
[0047] Tarot oil extraction yield test
[0048] Add 0.6% of the defoamer sample to 100g of black liquor. After desulfurization and acidification, dissolve the lignin in methanol-acetone solution, extract with petroleum ether, and evaporate to dryness to obtain tarro oil.
[0049] Table 1 Tarot Oil Extraction Data
[0050]
[0051] The test data above shows that the extraction rate of tarot oil using D1-D6 is significantly better than that using D7-D12.
[0052] Defoaming and foam-inhibiting performance test
[0053] First, add 600 mL of black liquor to the circulating bubbler, set the temperature to 85℃ and the flow rate to 6 L / min. Then, turn on the temperature control switch to heat the foaming liquid to the set temperature, and start the circulating pump to begin agitation and foaming. Once the foam reaches the 300 mL mark, add 0.2% defoamer and record the change in foam height over time. The better the performance of the defoamer, the lower the minimum mark the foam reaches; the better the foam suppression performance of the defoamer, the longer it takes for the foam to reach the 300 mL mark again.
[0054] Table 2. Defoaming and foam-suppressing performance of mineral oil defoamers at 25℃
[0055]
[0056] The test data above show that D1-D6 have significantly better defoaming and foam-suppressing properties than D7-D12.
Claims
1. A foam inhibitor with tall oil soap separation function, characterized in that, It is composed of the following components: 70-85% mineral oil, 5-15% silicone polyether, 1-8% main defoaming agent, and 5-15% synergist; The main defoaming substance is composed of waxy substances and silica, wherein the waxy substances account for 10-40% of the total mass of the main defoaming substance, and the silica accounts for 60-90% of the total mass of the main defoaming substance. The synergist is composed of fatty alcohol polyether and chiral monoterpene alcohol, wherein the chiral monoterpene alcohol accounts for 20-50% of the total mass of the synergist, and the fatty alcohol polyether accounts for 50-80% of the total mass of the synergist.
2. A foam inhibitor with tall oil soap separation function as described in claim 1, characterized in that, The mineral oil is selected from kerosene, diesel oil, white oil, and naphthenic oil, and can be used alone or in combination.
3. A foam inhibitor with tall oil soap separation function as described in claim 1, characterized in that, The structural formula of the silicone polyether is as follows: (CH3)3SiO{ ((CH3)2SiO x (CH3GSiO) y (CH3)2G The subscript x is an integer from 10 to 200; y is an integer from 5 to 30; G is a polyether group with the structural formula: -(CH2). z (EO) g (PO) h H, where the subscript z is an integer from 2 to 6, g is an integer from 20 to 100, and h is an integer from 1 to 20.
4. A foam inhibitor with tall oil soap separation function as described in claim 1, characterized in that, Among the main defoaming substances, the waxes are selected from waxes with a melting point of 30-120℃, including natural waxes, synthetic waxes, and mineral waxes, and account for 10-40% of the total mass of the main defoaming substances.
5. A foam inhibitor with tall oil soap separation function as described in claim 1, characterized in that, Among the main defoaming substances, the silica is hydrophobic silica with a specific surface area of 30–500 m². 2 / g; the dosage accounts for 60-90% of the total mass of the main defoaming substances.
6. A foam inhibitor with tall oil soap separation function as described in claim 1, characterized in that, The chiral monoterpene alcohol in the synergist is selected from rosin alcohol and menthol.
7. A foam inhibitor with tall oil soap separation function as described in claim 1, characterized in that, The fatty alcohol polyether in the synergist has the general structural formula R. 3 (OCH2CH2) m (OCH2CH(CH3)) n OH, R 3 It refers to straight-chain or branched alkyl, cycloalkyl, or aralkyl groups with 8-22 carbon atoms, where m is an integer from 1 to 50 and n is an integer from 10 to 100.
8. A foam inhibitor with tall oil soap separation function as described in claim 1, characterized in that, The preparation method of the foam inhibitor is as follows: (1) First, add mineral oil, silicone polyether and the main defoaming substance into the reaction flask. After adding, stir and heat to 80-150℃ and keep warm for 0.5-3 hours. (2) After the heat preservation is completed, cool down to 50-80℃, add the synergist, stir evenly and then homogenize the material; (3) Vacuum degassing to obtain the foam inhibitor.